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Kraft und Kognition
(2023)
Die in den letzten Jahren aus Querschnittstudien gewonnenen empirischen Erkenntnisse deuten auf einen Zusammenhang zwischen muskulärer Kraftleistungsfähigkeit und kognitiver Leistungsfähigkeit hin [10]. Diese Beobachtung wird von Längsschnittstudien gestützt, bei denen in Folge gezielter Krafttrainingsinterventionen, welche typischerweise zur Steigerung der muskulären Kraftleistungsfähigkeit führen, Verbesserungen der kognitiven Leistungsfähigkeit dokumentiert werden konnten [11]. Die zugrundeliegenden Mechanismen, die den Zusammenhang zwischen muskulärer Kraftleistungsfähigkeit und kognitiver Leistungsfähigkeit begründen, sind jedoch noch nicht vollständig bekannt und bedürfen weiterer Forschung [10,12]. Vor diesem Hintergrund hatten die im Rahmen dieser Dissertation durchgeführten Forschungsarbeiten das übergeordnete Ziel, die Mechanismen zu untersuchen, welche den Zusammenhang zwischen der muskulären Kraftleistungsfähigkeit und der kognitiven Leistungsfähigkeit erklären können. In dieser Arbeit wurden dazu unterschiedliche Populationen (junge Menschen und ältere Menschen ohne und mit leichten kognitiven Störungen) unter Anwendung verschiedener untersuchungsmethodischer Ansätze (systematische Literaturrecherche, Doppelaufgabenparadigma und funktionelle Nahinfrarotspektroskopie) untersucht. Aufgrund der im Rahmen dieser Dissertation durchgeführten Forschungsarbeiten, die konsekutiv aufeinander aufbauen, konnten folgende Haupterkenntnisse gewonnen werden:
• Um einen umfassenden Überblick über die aktuelle Evidenzlage zum Thema Kraftleistungsfähigkeit und kognitiver Leistungsfähigkeit sowie den zugrundeliegenden neuronalen Korrelaten zu erlangen, wurde eine systematische Literaturrecherche zu diesem Forschungsthema durchgeführt. Die Ergebnisse dieser systematischen Literaturrecherche dokumentieren, dass ein gezieltes Krafttraining neben der Steigerung der kognitiven Leistungsfähigkeit zu funktionellen und strukturellen Veränderungen des Gehirns, insbesondere in frontalen Gehirnregionen, führen kann [13]. Ferner zeigen die Ergebnisse dieser systematischen Literaturrecherche, bei der eine begrenzte Anzahl verfügbarer Studien (n = 18) identifiziert wurde, den Bedarf weiterer Forschungsarbeiten zu diesem Themenfeld an [13].
• Zur Überprüfung der Hypothese, dass zur Ausführung von Krafttrainingsübungen höhere kognitive Prozesse benötigt werden, wurde in einer experimentellen Studie bei jüngeren gesunden Erwachsenen das Doppelaufgabenparadigma bei der Krafttrainingsübung Knie-beuge angewendet. Die in dieser Studie beobachteten Doppelaufgabenkosten bei der Ausführung der Krafttrainingsübung Kniebeuge (im Vergleich zur Kontrollbedingung Stehen) deuten auf die Beteiligung höherer kognitiver Prozesse zur Lösung dieser Bewegungsaufgabe hin und bestätigen die aufgestellte Hypothese [14].
• Um die Hypothese zu untersuchen, dass spezifische neuronale Korrelate (funktionelle Gehirnaktivität) den Zusammenhang zwischen muskulärer Kraftleistungsfähigkeit und kognitiver Leistungsfähigkeit vermitteln, wurde bei jungen gesunden Erwachsenen der Zusammenhang zwischen der Ausprägung der maximalen Handgriffkraft (normalisiert auf den Body-Mass-Index) und der kortikalen hämodynamischen Antwortreaktion untersucht, die bei der Durchführung eines standardisierten kognitiven Tests mittels funktioneller Nahinfrarotspektroskopie in präfrontalen Gehirnarealen gemessen wurde. Im Rahmen dieser Querschnittsstudie konnte die initiale Hypothese nicht vollständig bestätigt werden, da zwar Zusammenhänge zwischen maximaler Handgriffkraft und kognitiver Leistungsfähigkeit mit Parametern der hämodynamischen Antwortreaktion beobachtet wurden, aber die Ausprägung der maximalen Handgriffkraft nicht im Zusammenhang mit der Kurzeitgedächtnisleistung stand [16].
• Zur Untersuchung der Annahme, dass eine vorliegende neurologische Erkrankung (im Speziellen eine leichte kognitive Störung), die typischerweise mit Veränderungen von spezifischen neuronalen Korrelaten (z.B. des Hippokampus‘ [17-19] und des präfrontalen Kortex‘ [20,21]) einhergeht, einen Einfluss auf die Assoziation zwischen muskulärer Kraftleistungsfähigkeit und kognitiver Leistungsfähigkeit hat, wurde in einer Querschnittsstudie der Zusammenhang zwischen der Ausprägung der maximalen Handgriffkraft (normalisiert auf den Body-Mass-Index) und der Ausprägung der exekutiven Funktionen bei älteren Erwachsenen mit amnestischem und nicht-amnestischem Subtyp der leichten kognitiven Störung sowie gesunden älteren Erwachsenen untersucht. In dieser Querschnittsstudie wurde nur bei älteren Erwachsenen mit dem amnestischen Subtyp der leichten kognitiven Störung ein Zusammenhang zwischen maximaler Handgriffkraft und exekutiven Funktionen beobachtet. Solch eine Korrelation existiert jedoch nicht bei älteren Erwachsenen mit dem non-amnestischen Subtyp der leichten kognitiven Störung oder bei gesunden älteren Erwachsenen [24].
• In einem Perspektivenartikel wurde aufgezeigt, wie durch die theoriegeleitete Nutzung physiologischer Effekte, die bei einer speziellen Krafttrainingsmethode durch die Moderation des peripheren Blutflusses mittels Manschetten oder Bändern auftreten, insbesondere Populationen mit niedriger mechanischer Belastbarkeit von den positiven Effekten des Krafttrainings auf die Gehirngesundheit profitieren könnten [25].
Insgesamt deuten die Ergebnisse der in dieser Dissertation zusammengeführten und aufeinander aufbauenden Forschungsarbeiten auf das Vorhandensein von gemeinsamen neuronalen Korrelaten (z.B. frontaler Kortex) hin, die sowohl für die muskuläre Kraftleistungsfähigkeit als auch für höhere kognitive Prozesse eine wichtige Rolle spielen [26]. Betrachtet man die in der vorliegenden Dissertation gewonnenen Erkenntnisse im Verbund mit den bereits in der Literatur existieren-den empirischen Belegen, unterstützen sie die Sichtweise, dass eine relativ hohe muskuläre Kraftleistungsfähigkeit und deren Erhalt durch gezielte Krafttrainingsinterventionen über die Lebenspanne positive Effekte auf die (Gehirn-)Gesundheit haben können [27].
Digital Fashion
(2024)
Das virtuelle Kleid als mediale und soziokulturelle Alltagserscheinung der Gegenwart bildet den Gegenstand der vorliegenden interdisziplinären Unter-suchung. An der Schnittstelle zwischen Menschen, Medien und Mode ist das virtuelle Kleid an unrealen Orten und in synthetischen Situationen ausschließlich auf einem Screen erfahrbar. In diesem Dispositiv lassen sich Körperkonzepte, Darstellungskonventionen, soziale Handlungsmuster und Kommunikations-strategien ausmachen, die zwar auf einer radikalen Ablösung vom textilen Material beruhen, aber dennoch nicht ohne sehr konkrete Verweise auf das textile Material auskommen. Dies führt zu neuen Ansätzen der Auseinandersetzung mit Kleidern, die nun als Visualisierung gebündelter Datenpakete zu betrachten sind. Die dynamische Entwicklung neuer Erscheinungsformen und deren nahtlose Einbindung in traditionelle Geschäftsmodelle und bestehende Modekonzepte macht eine Positionsbestimmung notwendig, insbesondere im Hinblick auf gegenwärtige Nachhaltigkeitsdiskurse um immaterielle Produkte. Für diese Studie liefern die hinter den Bildern liegenden Prozesse der ökonomischen Ausrichtung, der Herstellung, der Verwendung und der Rezeption den methodologischen Zugang für die Analyse. Mithilfe eines typologisierenden Instrumentariums wird aus der Vielzahl und Vielfalt der Darstellungen ein Set an forschungsleitenden Beispielen zusammengestellt, welche dann in einer mehrstufigen Kontextanalyse zu einer begrifflichen Fassung des virtuellen Kleides sowie zu fünf Kontexteinheiten führen. Am Beispiel des virtuellen Kleides zeichnet diese Untersuchung den technischen, gesellschaftlichen und sozialen Wandel nach und arbeitet seine Bedeutung für zukünftige Modeentwicklungen heraus. Damit leistet die Untersuchung einen Beitrag zur medien- und sozialwissenschaftlichen Modeforschung der Gegenwart.
Mountain ranges can fundamentally influence the physical and and chemical processes that shape Earths’ surface. With elevations of up to several kilometers they create climatic enclaves by interacting with atmospheric circulation and hydrologic systems, thus leading to a specific distribution of flora and fauna. As a result, the interiors of many Cenozoic mountain ranges are characterized by an arid climate, internally drained and sediment-filled basins, as well as unique ecosystems that are isolated from the adjacent humid, low-elevation regions along their flanks and forelands. These high-altitude interiors of orogens are often characterized by low relief and coalesced sedimentary basins, commonly referred to as plateaus, tectono-geomorphic entities that result from the complex interactions between mantle-driven geological and tectonic conditions and superposed atmospheric and hydrological processes. The efficiency of these processes and the fate of orogenic plateaus is therefore closely tied to the balance of constructive and destructive processes – tectonic uplift and erosion, respectively. In numerous geological studies it has been shown that mountain ranges are delicate systems that can be obliterated by an imbalance of these underlying forces. As such, Cenozoic mountain ranges might not persist on long geological timescales and will be destroyed by erosion or tectonic collapse. Advancing headward erosion of river systems that drain the flanks of the orogen may ultimately sever the internal drainage conditions and the maintenance of storage of sediments within the plateau, leading to destruction of plateau morphology and connectivity with the foreland. Orogenic collapse may be associated with the changeover from a compressional stress field with regional shortening and topographic growth, to a tensional stress field with regional extensional deformation and ensuing incision of the plateau. While the latter case is well-expressed by active extensional faults in the interior parts of the Tibetan Plateau and the Himalaya, for example, the former has been attributed to have breached the internally drained areas of the high-elevation sectors of the Iranian Plateau.
In the case of the Andes of South America and their internally drained Altiplano-Puna Plateau, signs of both processes have been previously described. However, in the orogenic collapse scenario the nature of the extensional structures had been primarily investigated in the northern and southern terminations of the plateau; in some cases, the extensional faults were even regarded to be inactive. After a shallow earthquake in 2020 within the Eastern Cordillera of Argentina that was associated with extensional deformation, the state of active deformation and the character of the stress field in the central parts of the plateau received renewed interest to explain a series of extensional structures in the northernmost sectors of the plateau in north-western Argentina. This study addresses (1) the issue of tectonic orogenic collapse of the Andes and the destruction of plateau morphology by studying the fill and erosion history of the central eastern Andean Plateau using sedimentological and geochronological data and (2) the kinematics, timing and magnitude of extensional structures that form well-expressed fault scarps in sediments of the regional San Juan del Oro surface, which is an integral part of the Andean Plateau and adjacent morphotectonic provinces to the east.
Importantly, sediment properties and depositional ages document that the San Juan del Oro Surface was not part of the internally-drained Andean Plateau, but rather associated with a foreland-directed drainage system, which was modified by the Andean orogeny and that became successively incorporated into the orogen by the eastward-migration of the Andean deformation front during late Miocene – Pliocene time. Structural and geomorphic observations within the plateau indicate that extensional processes must have been repeatedly active between the late Miocene and Holocene supporting the notion of plateau-wide extensional processes, potentially associated with Mw ~ 7 earthquakes. The close relationship between extensional joints and fault orientations underscores that 3 was oriented horizontally in NW-SE direction and 1 was vertical. This unambiguously documents that the observed deformation is related to gravitational forces that drive the orogenic collapse of the plateau. Applied geochronological analyses suggest that normal faulting in the northern Puna was active at about 3 Ma, based on paired cosmogenic nuclide dating of sediment fill units. Possibly due to regional normal faulting the drainage system within the plateau was modified, promoting fluvial incision.
Die Geschichtsschreibung terminiert das Ende des deutschen Zionismus bisher mit dem NS-Verbot der Zionistischen Vereinigung für Deutschland im Zuge des Novemberpogroms 1938. Zu diesem Zeitpunkt hatte er aber von seinem geographischen Kontext entgrenzt, in Erez Israel bereits neue Wurzeln geschlagen. Zionisten aus Deutschland schickten sich nun an, mit ihrem spezifischen Erfahrungshorizont und Wertemaßstab und mitgebrachtem ideologischen Rüstzeug die Entwicklung des jüdischen Nationalheims mitzugestalten und einer umfassenden ökonomischen, kulturellen und politischen Akkulturation der deutschen Alijah den Weg zu bahnen. Entgegen aller zionistischen Theorie gründeten sie auf landsmannschaftlicher Basis im Jahr 1932 die Selbsthilfeorganisation Hitachduth Olej Germania und während des Weltkrieges die Partei Alija Chadascha.
Die Dissertation beinhaltet die Gesamtschau des deutschen Zionismus in seiner letzten Phase in den Jahren 1932 bis 1948; zugleich beleuchtet sie die Geschichte der etwa 60.000 in Palästina eingewanderten Juden aus Deutschland in der für diese Abhandlung relevanten Zeitperiode. Im ersten Teil wird in chronologischer Folge die 1932 beginnende letztmalige Sammlung und Neuformierung des deutschen Zionismus in seiner neu-alten Heimat dargestellt. Wenn man so will, die formativen Jahre im personellen, organisatorischen und ideologisch-politischen Sinne, die schließlich nach dem fast gänzlichen Scheitern der politischen Integration der deutschen Alijah mit der – in der Rückschau – fast zwangsläufig erscheinenden Begründung der Alija Chadascha ihren Abschluss fanden. Im zweiten Teil werden die Positionen der deutschen Zionisten zu den existenziellen Fragen der jüdischen Gemeinschaft in Palästina, hebräisch Jischuw genannt, in der im Fokus stehenden Zeitperiode dargestellt. Im Einzelnen handelt es sich erstens um die Einwanderungsfrage, die untrennbar verbunden war mit der in der zionistischen Theorie unabdingbaren Forderung nach der Erlangung einer jüdischen Majorität in Palästina; zweitens um die der staatlichen Ausgestaltung des zukünftigen jüdischen Gemeinwesens und drittens um die Frage der adäquaten Reaktion des Jischuw auf die Schoah. In diese jeweils in separaten Kapiteln behandelten Themenkomplexe wird die Frage nach dem anzustrebenden Verhältnis zur britischen Mandatsmacht mit einfließen. Hieran mussten die deutschen Zionisten ihr mitgebrachtes geistig-ideologisches Rüstzeug einem Praxistest unterziehen und nach realpolitischen Antworten suchen.
Dem kometenhaften Aufstieg der weiterhin landsmannschaftlich geprägten Alija Chadascha folgte dann in den ersten Nachkriegsjahren ein ebenso rapider Zerfall. Einige Monate nach der Staatsgründung Israels löste sie sich dann sang- und klanglos auf und das Gros ihrer Aktivisten integrierte sich in das Parteiengefüge des neuen Staates. Der deutsche Zionismus als politische Bewegung kam nun wirklich an sein Ende. Diese Abhandlung wird somit zum einen den Kampf der deutschen Alijah um gesellschaftliche Anerkennung und politische Partizipation im Jischuw nachzeichnen und zum anderen eine geistig-ideologische Verortung des deutschen Zionismus in seiner letzten Phase vollziehen und Tendenzen der ideologischen Neuausrichtung offenlegen. Darüber hinaus werden in der Historiographie vorhandene Allgemeinplätze wie die fast allseits anerkannte These vom Scheitern der deutschen Zionisten in der neuen Heimat einer Überprüfung unterzogen. Die letzte vorhandene Leerstelle im wissenschaftlichen Kanon zur mehr als 50-jährigen Geschichte des deutschen Zionismus wird somit geschlossen.
Die Fluoreszenz-Calcium-Imaging-Methode wird auch heute noch als gängige Methode verwendet, vor allem wegen der geringeren Kosten für das Wirkstoffscreening in der pharmazeutischen Forschung, wobei Ionenkanäle sowie einige der G-Protein gekoppelte Rezeptoren (GPCRs) die Mehrzahl der Wirkstoffziele ansprechen. Die zellfreie Synthese eukaryotischer Proteine hat nicht die Nachteile, die bei der Überexpression dieser ionenpermeablen Proteine in Zellen auftreten können, wie z. B. Zelltoxizität, geringere Proteinexpression und die Beseitigung der exprimierten Proteine aufgrund veränderter Domänen sowie die zeitaufwändige Pflege von Zelllinien. Die Synthese von Ionenkanälen in zellfreien Proteinsyntheseplattformen für das künftige Wirkstoffscreening ist noch in der Grundlagenforschung. Obwohl die Fluoreszenz-Calcium-Imaging-Methode in zellbasierten Assays weit verbreitet ist, wurde diese Methode bisher noch nicht in zellfreien Proteinexpressionssystemen verwendet. Insgesamt ist die neue Anwendung der Calcium-Imaging-Methode in eukaryontischen zellfreien Systemen eine Voraussetzung für die schnelle pharmakologische Analyse von Wirkstoffen. Das erste Ziel dieser wissenschaftlichen Arbeit bestand darin, die grundlegenden Prinzipien der Calcium-Imaging-Methode zur Untersuchung von Ionenkanälen in zellbasierten Systemen zu untersuchen. Hierfür wurden zwei Tumorzelllinien des Auges verwendet, und zwar benigne Pterygiumzellen und maligne Aderhautmelanom 92.1 Zellen. In diesen Studien wurde die Interaktion zwischen den nativ überexprimierten transient-receptor-potential-Ionenkanälen (TRPs) wie TRP Vanilliod 1 (TRPV1) (Capsaicinrezeptor) und TRP Melastatin 8 (TRPM8) (Mentholrezeptor) in diesen Tumorzellen nach Zugabe von verschiedenen Medikamenten und Hormonen untersucht. Das zweite Ziel dieser Arbeit war es, den Calcium-Mechanismus von GPCRs in den Zellen zu untersuchen. Zu diesem Zweck wurde Mas, ein GPCR und Angiotensin (1-7) -Hormonrezeptor, aus dem renin-angiotensin-aldosteron-system (RAAS) in der Human Embryonic Kidney-293 (HEK293) Zelllinie überexprimiert. In dieser Studie wurden insbesondere die Aktivierung klassischer GPCR-Signalwege wie Phospholipase C und Proteinkinase C durch Angiotensin-(1-7) über Mas und die Beteiligung von TRP-Kanälen nachgewiesen. Die zellbasierte-Calcium-Imaging-Methode für chemische Calcium-Indikatoren ließ sich aufgrund der Anwesenheit einer großen Menge cytosolischer Carboxylesterasen gut anwenden. Carboxylesterase ist das wichtigste Enzym in der Calcium Imaging Methode, das die Verarbeitung chemischen Calcium-Farbstoffe behandelt. Dieses Enzym fehlt jedoch in Mikrosomen, die als Basismembran für die Integration synthetisierter Ionenkanäle in eukaryontischen zellfreien Systemen verwendet werden. Das dritte Ziel dieser Forschungsarbeit war die Umsetzung der zellbasierten Calcium-Imaging Methode und der Calcium-Signalwege in zellfreie Systeme. Hier wurde die zellfrei synthetisierte Carboxylesterase in Mikrosomen von Spodoptera frugiperda (Sf21) als praktikables Calcium-Imaging-Werkzeug etabliert, um sowohl native ionenpermeable Proteine als auch zellfrei-synthetisierte Ionenkanäle zu untersuchen. Die Enzymaktivität der zellfrei-synthetisierten Carboxylesterase in Mikrosomen wurde durch Esterase-Assays und den Calcium-Fluoreszenzfarbstoff Fluo-5N Acetoxymethylester (Fluo-5N AM) Belastungstests nachgewiesen. Das Calcium-Imaging der nativ vorhandenen Ca2+-ATPase des sarkoplasmatischen/endoplasmatischen Retikulums (SERCA) und der Ryanodin-Rezeptoren (RyR) in den Mikrosomen sowie der zell-frei exprimierten TRP-Ionenkanäle wurden mit dem Fura-5N-AM- Fluoreszenzfarbstoff in mit Carboxylesterase vorsynthetisierten Mikrosomen nachgewiesen.
Zusammenfassend lässt sich sagen, dass das Prinzip der zellbasierten Calcium-Imaging -Methode vielversprechend an das eukaryotische zellfreie Sf21-System angepasst werden konnte, um Ionenkanäle zu analysieren. Nach entsprechender Forschung könnte die etablierte Methode in Zukunft auch auf andere Membranproteine ausgeweitet werden. Dies umfasst die Untersuchung anderer zell-frei exprimierte GPCRs oder anderer Ionenkanäle wie Kalium-, Natrium- und Chlorid-Ionenkanäle.
Advancements in computer vision techniques driven by machine learning have facilitated robust and efficient estimation of attributes such as depth, optical flow, albedo, and shading. To encapsulate all such underlying properties associated with images and videos, we evolve the concept of intrinsic images towards intrinsic attributes. Further, rapid hardware growth in the form of high-quality smartphone cameras, readily available depth sensors, mobile GPUs, or dedicated neural processing units have made image and video processing pervasive. In this thesis, we explore the synergies between the above two advancements and propose novel image and video processing techniques and systems based on them. To begin with, we investigate intrinsic image decomposition approaches and analyze how they can be implemented on mobile devices. We propose an approach that considers not only diffuse reflection but also specular reflection; it allows us to decompose an image into specularity, albedo, and shading on a resource constrained system (e.g., smartphones or tablets) using the depth data provided by the built-in depth sensors. In addition, we explore how on-device depth data can further be used to add an immersive dimension to 2D photos, e.g., showcasing parallax effects via 3D photography. In this regard, we develop a novel system for interactive 3D photo generation and stylization on mobile devices. Further, we investigate how adaptive manipulation of baseline-albedo (i.e., chromaticity) can be used for efficient visual enhancement under low-lighting conditions. The proposed technique allows for interactive editing of enhancement settings while achieving improved quality and performance. We analyze the inherent optical flow and temporal noise as intrinsic properties of a video. We further propose two new techniques for applying the above intrinsic attributes for the purpose of consistent video filtering. To this end, we investigate how to remove temporal inconsistencies perceived as flickering artifacts. One of the techniques does not require costly optical flow estimation, while both provide interactive consistency control. Using intrinsic attributes for image and video processing enables new solutions for mobile devices – a pervasive visual computing device – and will facilitate novel applications for Augmented Reality (AR), 3D photography, and video stylization. The proposed low-light enhancement techniques can also improve the accuracy of high-level computer vision tasks (e.g., face detection) under low-light conditions. Finally, our approach for consistent video filtering can extend a wide range of image-based processing for videos.
Zwischen Modellierung und Stakeholderbeteiligung - Wissensproduktion in der Energiewendeforschung
(2023)
Die Dekarbonisierung des Energiesystems ist Teil der international im Rahmen des Pariser Klimaabkommens beschlossenen CO2-Minderungsstrategie zur Bekämpfung des Klimawandels. Nach den Verhandlungen und Beschlüssen der Klimaziele stehen politische Entscheider weltweit nun vor der Frage, wie sie diese erreichen können. Dies produziert eine hohe politische Nachfrage nach Wissen um die direkten und indirekten Effekte verschiedener Instrumente und potentiellen Entwicklungspfade einer Energiewende. Dieser gesellschaftliche Bedarf an wissenschaftlichen Antworten zu Lösungsoptionen wurde im Rahmen einer Klimafolgenforschung, genauer einer Klimapolitikfolgenforschung, aufgenommen. Der relativ neue Zweig einer Energiewendeforschung hat sich weltweit entwickelt, steht dabei allerdings vor der doppelten Herausforderung: Erstens befindet sich das Objekt der Forschung nicht im luftleeren Raum, sondern innerhalb ökonomischer, sozialer und politischer Zusammenhänge, hier gesellschaftliche Einbettung genannt. Denn die Frage, wie die Energiewende erreicht werden kann, wird auch außerhalb der Wissenschaft debattiert und stellt damit ein Aushandlungsfeld unterschiedlicher Interessen und Narrative dar. Zweitens befindet sich das zu untersuchende Objekt in der Zukunft, hier unter dem Terminus des strukturellen Nicht-Wissens zusammengefasst. Diese beiden Bedingungen führen dazu, dass konventionelle Methoden der empirischen Sozialforschung nicht greifen und eine Öffnung und Transformation der Wissenschaft in Hinblick auf neue Methoden vonnöten ist (Nowotny 2001, Ravetz 2006, Schneidewind 2013). In dieser Arbeit untersuche ich zwei Möglichkeiten, wie mit der Herausforderung, Wissen unter der Bedingung des strukturellen Nicht-Wissens und der gesellschaftlichen Einbettung zu produzieren, in der Energiewendeforschung umgegangen wird. Einerseits wird dies durch die Einbeziehung von Stakeholdern, also nicht-wissenschaftlicher Akteure, in den Forschungsprozess getan. Andererseits ist die Nutzung von komplexen ökonometrischen Modellen zur Berechnung von Implikationen und energiewirtschaftlichen Entwicklungspfaden zu einem zentralen Mittel der Wissensgenerierung in der Energiewendeforschung avanciert. Damit wird der als Problem verstandenen strukturellen Bedingung des Nicht-Wissens insofern begegnet, als dass die Ergebnisse von Stakeholder-Involvement und von Modellierungsarbeiten zweifelsohne neues Wissen zur Verfügung stellen. Uneinigkeit besteht jedoch darin, worüber dieses Wissen etwas aussagt: Sind es Interessen oder legitime Perspektiven, die Stakeholder in den Forschungsprozess einbringen und sind Modelle vereinfachte Darstellungen der Welt oder sind sie Ausdruck der Vorstellung des Modellierers?
El plateau Andino es el segundo plateau orogénico más grande del mundo y se ubica en los Andes Centrales, desarrollado en un sistema orogénico no colisional. Se extiende desde el sur del Perú (15°S), hasta el norte de Argentina y Chile (27°30´S). A partir de los 24°S y prologándose hacia el sur, el plateau Andino se denomina Puna y está caracterizado por un sistema de cuencas endorreicas y salares delimitados por cordones montañosos. Entre los 26° y 27°30´S, la Puna encuentra su límite austral en una zona de transición entre una zona de subducción normal y una zona de subducción plana o “flat slab” que se prolonga hasta los 33°S. Diversos estudios documentan la ocurrencia de un aumento del espesor cortical, y levantamiento episódico y diacrónico del relieve, alcanzando su configuración actual durante el Mioceno tardío. Posteriormente, el plateau habría experimentado un cambio en el estilo de deformación dominado por procesos extensionales evidenciado por fallas y terremotos de cinemática normal. Sin embargo, en el borde sur del plateau de la Puna y en las áreas delimitadas con el resto del orógeno, la variación del campo de esfuerzo no está del todo comprendida, reflejando una excelente oportunidad para evaluar cómo el campo de esfuerzo puede evolucionar durante el desarrollo del orógeno y cómo puede verse afectado por la presencia/ausencia de un plateau orogénico, así como también por la existencia de anisotropías estructurales propias de cada unidad morfotectónica.
Esta Tesis investiga la relación entre la deformación cortical somera y la evolución en tiempo y espacio del campo de esfuerzos en el sector sur del plateau Andino, durante el cenozoico tardío. Para realizar esta investigación, se utilizaron técnicas de obtención de edades radiométricas con el método Uranio-Plomo (U-Pb), análisis de fallas mesoscópicas para la obtención de tensores de esfuerzos y delimitación de la orientación de los ejes principales de esfuerzos, análisis de anisotropía de susceptibilidad magnética en rocas sedimentarias y volcanoclásticas para estimar direcciones de acortamiento o direcciones de transporte sedimentario, técnicas de modelado cinemático para llegar a una aproximación de las estructuras corticales profundas asociadas a la deformación allí registrada, y un análisis morfométrico para la identificación de indicadores geomorfológicos asociados a deformación producto de la actividad tectónica cuaternaria.
Combinando estos resultados con los antecedentes previamente documentados, el estudio revela una compleja variación del campo de esfuerzo caracterizado por cambios en la orientación y permutaciones verticales de los ejes principales de esfuerzos, durante cada régimen de deformación, durante los últimos ~24 Ma. La evolución del campo de esfuerzos puede ser asociada temporalmente a tres fases orogénicas involucradas con la evolución de los Andes Centrales en esta latitud: (1) una primera fase con un régimen de esfuerzos compresivos de acortamiento E-O documentado desde el Eoceno, Oligoceno tardío hasta el Mioceno medio en el área, coincide con la fase de construcción andina, engrosamiento y crecimiento de la corteza y levantamiento topográfico; (2) una segunda fase caracterizada por un régimen de esfuerzos de transcurrencia, a partir de los ~11 Ma en el borde occidental y compresión y transcurrencia a los~5 Ma en el borde oriental del plateau de la Puna, y un régimen de esfuerzo compresivos en Famatina y las Sierras Pampeanas interpretado como una transición entre la construcción orogénica del Neógeno y la máxima acumulación de deformación y el alzamiento topográfico del plateau de la Puna, y (3) una tercera fase donde el régimen se caracteriza por la transcurrencia en la Puna y en su borde occidental y en su borde oriental con las Sierras Pampeanas, después de ~5-4 Ma, interpretado como un régimen de esfuerzos controlados por el engrosamiento cortical desarrollado a lo largo del borde sur del plateau Altiplano/Puna, previo a un colapso orogénico. Los resultados dejan en evidencia que el borde del plateau experimentó el paso desde un régimen compresivo hacia uno transcurrente, que se diferencia de la extensión documentada hacia el norte en el plateau Andino para el mismo período. Cambios en los esfuerzos similares han sido documentado durante la construcción del plateau Tibetano, en donde un régimen de esfuerzo predominantemente compresivo cambió a un régimen de transcurrente cuando el plateau habría alcanzado la mitad de su elevación actual, y que posteriormente derivó en un régimen extensional, entre 14 y 4 Ma, cuando la altitud del plateau fue superior al 80% respecto a su actitud actual, lo que podría estar indicando que los regímenes transcurrentes representan etapas transicionales entre las zonas externas del plateau bajo compresión y las zonas internas, en las que los regímenes extensionales son más viables de ocurrir.
Lanthanide based ceria nanomaterials are important practical materials due to their redox properties that are useful in technology and life sciences. This PhD thesis examined various properties and potential for catalytic and bio-applications of Ln3+-doped ceria nanomaterials. Ce1-xGdxO2-y: Eu3+, gadolinium doped ceria (GDC) (0 ≤ x ≤ 0.4) nanoparticles were synthesized by flame spray pyrolysis (FSP) and studied, followed by 15 % CexZr1-xO2-y: Eu3+|YSZ (0 ≤ x ≤ 1) nanocomposites. Furthermore, Ce1-xYb xO2-y (0.004 ≤ x ≤ 0.22) nanoparticles were synthesized by thermal decomposition and characterized. Finally, CeO2-y: Eu3+ nanoparticles were synthesized by a microemulsion method, biofunctionalized and characterized. The studies undertaken presents a novel approach to structurally elucidate ceria-based nanomaterials by way of Eu3+ and Yb3+ spectroscopy and processing the spectroscopic data with the multi-way decomposition method PARAFAC. Data sets of the three variables: excitation wavelength, emission wavelength and time were used to perform the deconvolution of spectra.
GDC nanoparticles from FSP are nano-sized and of roughly cubic shape and crystal structure (Fm3̅m). Raman data revealed four vibrational modes exhibited by Gd3+ containing samples whereas CeO2-y: Eu3+ displays only two. The room temperature, time-resolved emission spectra recorded at λexcitation = 464 nm show that Gd3+ doping results in significantly altered emission spectra compared to pure ceria. The PARAFAC analysis for the pure ceria samples reveals two species; a high-symmetry species and a low-symmetry species. The GDC samples yield two low-symmetry spectra in the same experiment. High-resolution emission spectra recorded at 4 K after probing the 5D0-7F0 transition revealed additional variation in the low symmetry Eu3+ sites in pure ceria and GDC. The data of the Gd3+-containing samples indicates that the average charge density around the Eu3+ ions in the lattice is inversely related to Gd3+ and oxygen vacancy concentration.
The particle crystallites of the 773 K and 1273 K annealed Yb3+ -ceria nanostructure materials are nano-sized and have a cubic fluorite structure with four Raman vibrational modes. Elemental maps clearly show that cluster formation occurs for 773 K annealed with high Yb3+ ion concentration from 15 mol % in the ceria lattice. These clusters are destroyed with annealing to 1273 K. The emission spectra observed from room temperature and 4 K measurements for the Ce1-xYb xO2-y samples have a manifold that corresponds to the 2F5/2-2F7/2 transition of Yb3+ ions. Some small shifts are observed in the Stark splitting pattern and are induced by the variations of the crystal field influenced by where the Yb3+ ions are located in the crystal lattices in the samples. Upon mixing ceria with high Yb3+ concentrations, the 2F5/2-2F7/2 transition is also observed in the Stark splitting pattern, but the spectra consist of two broad high background dominated peaks. Annealing the nanomaterials at 1273 K for 2 h changes the spectral signature as new peaks emerge. The deconvolution yielded luminescence decay kinetics as well as the accompanying luminescence spectra of three species for each of the low Yb3+ doped ceria samples annealed at 773 K and one species for the 1273 K annealed samples. However, the ceria samples with high Yb3+ concentration annealed at the two temperatures yielded one species with lower decay times as compared to the Yb3+ doped ceria samples after PARAFAC analysis.
Through the calcination of the nanocomposites at two high temperatures, the evolution of the emission patterns from specific Eu3+ lattice sites to indicate structural changes for the nanocomposites was followed. The spectroscopy results effectively complemented the data obtained from the conventional techniques. Annealing the samples at 773 K, resulted in amorphous, unordered domains whereas the TLS of the 1273 K nanocomposites reveal two distinct sites, with most red shifted Eu3+ species coming from pure Eu3+ doped ZrO2 on the YSZ support.
Finally, for Eu3+ doped ceria, successful transfer from hydrophobic to water phase and subsequent biocompatibility was achieved using ssDNA. PARAFAC analysis for the Eu3+ in nanoparticles dispersed in toluene and water revealed one Eu3+ species, with slightly differing surface properties for the nanoparticles as far as the luminescence kinetics and solvent environments were concerned. Several functionalized nanoparticles conjugated onto origami triangles after hybridization were visualized by atomic force microscopy (AFM). Putting all into consideration, Eu3+ and Yb3+ spectroscopy was used to monitor the structural changes and determining the feasibility of the nanoparticle transfer into water. PARAFAC proves to be a powerful tool to analyze lanthanide spectra in crystalline solid materials and in solutions, which are characterized by numerous Stark transitions and where measurements usually yield a superposition of different emission contributions to any given spectrum.
Earthquake modeling is the key to a profound understanding of a rupture. Its kinematics or dynamics are derived from advanced rupture models that allow, for example, to reconstruct the direction and velocity of the rupture front or the evolving slip distribution behind the rupture front. Such models are often parameterized by a lattice of interacting sub-faults with many degrees of freedom, where, for example, the time history of the slip and rake on each sub-fault are inverted. To avoid overfitting or other numerical instabilities during a finite-fault estimation, most models are stabilized by geometric rather than physical constraints such as smoothing.
As a basis for the inversion approach of this study, we build on a new pseudo-dynamic rupture model (PDR) with only a few free parameters and a simple geometry as a physics-based solution of an earthquake rupture. The PDR derives the instantaneous slip from a given stress drop on the fault plane, with boundary conditions on the developing crack surface guaranteed at all times via a boundary element approach. As a side product, the source time function on each point on the rupture plane is not constraint and develops by itself without additional parametrization. The code was made publicly available as part of the Pyrocko and Grond Python packages. The approach was compared with conventional modeling for different earthquakes. For example, for the Mw 7.1 2016 Kumamoto, Japan, earthquake, the effects of geometric changes in the rupture surface on the slip and slip rate distributions could be reproduced by simply projecting stress vectors. For the Mw 7.5 2018 Palu, Indonesia, strike-slip earthquake, we also modelled rupture propagation using the 2D Eikonal equation and assuming a linear relationship between rupture and shear wave velocity. This allowed us to give a deeper and faster propagating rupture front and the resulting upward refraction as a new possible explanation for the apparent supershear observed at the Earth's surface.
The thesis investigates three aspects of earthquake inversion using PDR: (1) to test whether implementing a simplified rupture model with few parameters into a probabilistic Bayesian scheme without constraining geometric parameters is feasible, and whether this leads to fast and robust results that can be used for subsequent fast information systems (e.g., ground motion predictions). (2) To investigate whether combining broadband and strong-motion seismic records together with near-field ground deformation data improves the reliability of estimated rupture models in a Bayesian inversion. (3) To investigate whether a complex rupture can be represented by the inversion of multiple PDR sources and for what type of earthquakes this is recommended.
I developed the PDR inversion approach and applied the joint data inversions to two seismic sequences in different tectonic settings. Using multiple frequency bands and a multiple source inversion approach, I captured the multi-modal behaviour of the Mw 8.2 2021 South Sandwich subduction earthquake with a large, curved and slow rupturing shallow earthquake bounded by two faster and deeper smaller events. I could cross-validate the results with other methods, i.e., P-wave energy back-projection, a clustering analysis of aftershocks and a simple tsunami forward model.
The joint analysis of ground deformation and seismic data within a multiple source inversion also shed light on an earthquake triplet, which occurred in July 2022 in SE Iran. From the inversion and aftershock relocalization, I found indications for a vertical separation between the shallower mainshocks within the sedimentary cover and deeper aftershocks at the sediment-basement interface. The vertical offset could be caused by the ductile response of the evident salt layer to stress perturbations from the mainshocks.
The applications highlight the versatility of the simple PDR in probabilistic seismic source inversion capturing features of rather different, complex earthquakes. Limitations, as the evident focus on the major slip patches of the rupture are discussed as well as differences to other finite fault modeling methods.
Supernova remnants are considered to be the primary sources of galactic cosmic rays. These cosmic rays are assumed to be accelerated by the diffusive shock acceleration mechanism, specifically at shocks in the remnants. Particularly in the core-collapse scenario, these supernova remnant shocks expand inside the wind-blown bubbles structured by massive progenitors during their lifetime. Therefore, the complex environment of wind bubbles can influence the particle acceleration and radiation from the remnants. Further, the evolution of massive stars depends on their Zero Age Main Sequence mass, rotation, and metallicity. Consequently, the structures of the wind bubbles generated during the lifetime of massive stars should be considerably different. Hence, the particle acceleration in the core-collapse supernova remnants should vary, not only from the remnants evolving in the uniform environment but also from one another, depending on their progenitor stars.
A core-collapse supernova remnant with a very massive 60 𝑀 ⊙ progenitor star has been considered to study the particle acceleration at the shock considering Bohm-like diffusion. This dissertation demonstrates the modification in particle acceleration and radiation while the remnant propagates through different regions of the wind bubble by impacts from the profiles of gas density, the temperature of the bubble and the magnetic field structure. Subsequently, in this thesis, I discuss the impacts of the non-identical ambient environment of core-collapse supernova remnants on particle spectra and the non-thermal emissions, considering 20 𝑀 ⊙ and 60 𝑀⊙ massive progenitors having different evolutionary tracks. Additionally, I also analyse the effect of cosmic ray streaming instabilities on particle spectra.
To model the particle acceleration in the remnants, I have performed simulations in one-dimensional spherical symmetry using RATPaC code. The transport equation for cosmic rays and magnetic turbulence in test-particle approximation, along with the induction equation for the evolution of the large-scale magnetic field, have been solved simultaneously with the hydrodynamic equations for the expansion of remnants inside the pre-supernova circumstellar medium.
The results from simulations describe that the spectra of accelerated particles in supernova remnants are regulated by density fluctuations, temperature variations, the large-scale magnetic field configuration and scattering turbulence. Although the diffusive shock acceleration mechanism at supernova remnant shock predicts the spectral index of 2 for the accelerated non-thermal particles, I have obtained the particle spectra that deviate from this prediction, in the core-collapse scenario. I have found that the particle spectral index reaches 2.5 for the supernova remnant with 60 𝑀 ⊙ progenitor when the remnant resides inside the shocked wind region of the wind bubble, and this softness persists at later evolutionary stages even with Bohm-like diffusion for accelerated particles. However, the supernova remnant with 20 𝑀 ⊙ progenitor does not demonstrate persistent softness in particle spectra from the influence of the hydrodynamics of the corresponding wind bubble. At later stages of evolution, the particle spectra illustrate softness at higher energies for both remnants as the consequence of the escape of high-energy particles from the remnants while considering the cosmic ray streaming instabilities. Finally, I have probed the emission morphology of remnants that varies depending on the progenitors, particularly in earlier evolutionary stages. This dissertation provides insight into different core-collapse remnants expanding inside wind bubbles, for instance, the calculated gamma-ray spectral index from the supernova remnant with 60 𝑀 ⊙ progenitor at later evolutionary stages is consistent with that of the observed supernova remnants expanding in dense molecular clouds.
Conservation of the jaguar relies on holistic and transdisciplinary conservation strategies that integratively safeguard essential, connected habitats, sustain viable populations and their genetic exchange, and foster peaceful human-jaguar coexistence. These strategies define four research priorities to advance jaguar conservation throughout the species’ range. In this thesis I provide several relevant ecological and sociological insights into these research priorities, each addressed in a separate chapter. I focus on the effects of anthropogenic landscapes on jaguar habitat use and population gene flow, spatial patterns of jaguar habitat suitability and functional population connectivity, and on innovative governance approaches which can work synergistically to help achieve human-wildlife conviviality. Furthermore, I translate these insights into recommendations for conservation practice by providing tools and suggestions that conservation managers and stakeholders can use to implement local actions but also make broad scale conservation decisions in Central America. In Chapter 2, I model regional habitat use of jaguars, producing spatially-explicit maps for management of key areas of habitat suitability. Using an occupancy model of 13-year-camera-trap occurrence data, I show that human influence has the strongest impact on jaguar habitat use, and that Jaguar Conservation Units are the most important reservoirs of high quality habitat in this region. I build upon these results by zooming in to an area of high habitat suitability loss in Chapter 3, northern Central America. Here I study the drivers of jaguar gene flow and I produce spatially-explicit maps for management of key areas of functional population connectivity in this region. I use microsatellite data and pseudo-optimized multiscale, multivariate resistance surfaces of gene flow to show that jaguar gene flow is influenced by environmental, and even more strongly, by human influence variables; and that the areas of lowest gene flow resistance largely coincide with the location of the Jaguar Conservation Units. Given that human activities significantly impact jaguar habitat use and gene flow, securing viable jaguar populations in anthropogenic landscapes also requires fostering peaceful human-wildlife coexistence. This is a complex challenge that cannot be met without transdisciplinary academic research and cross-sectoral, collaborative governance structures that effectively respond to the multiple challenges of such coexistence. With this in mind, I focus in Chapter 4 on carnivore conservation initiatives that apply transformative governance approaches to enact transformative change towards human-carnivore coexistence. Using the frameworks of transformative biodiversity governance and convivial conservation, I highlight in this chapter concrete pathways, supported by more inclusive, democratic forms of conservation decision-making and participation that promote truly transformative changes towards human-jaguar conviviality.
Feminist Solidarities after Modulation produces an intersectional analysis of transnational feminist movements and their contemporary digital frameworks of identity and solidarity. Engaging media theory, critical race theory, and Black feminist theory, as well as contemporary feminist movements, this book argues that digital feminist interventions map themselves onto and make use of the multiplicity and ambiguity of digital spaces to question presentist and fixed notions of the internet as a white space and technologies in general as objective or universal. Understanding these frameworks as colonial constructions of the human, identity is traced to a socio-material condition that emerges with the modernity/colonialism binary. In the colonial moment, race and gender become the reasons for, as well as the effects of, technologies of identification, and thus need to be understood as and through technologies. What Deleuze has called modulation is not a present modality of control, but is placed into a longer genealogy of imperial division, which stands in opposition to feminist, queer, and anti-racist activism that insists on non-modular solidarities across seeming difference. At its heart, Feminist Solidarities after Modulation provides an analysis of contemporary digital feminist solidarities, which not only work at revealing the material histories and affective ""leakages"" of modular governance, but also challenges them to concentrate on forms of political togetherness that exceed a reductive or essentialist understanding of identity, solidarity, and difference.
Die Studie untersucht, wie Lehrpersonen auf Primarstufe ihre Anleitungsstrategien bei der Durchführung von musikalischen Gestaltungsprozessen in ihren Schulklassen entwickeln. Die Entwicklungsprozesse wurden vom Forscher begleitet und mit Reflexionsimpulsen unterstützt. Lehrende und Forscher analysieren und diskutieren regelmässig das Unterrichtsgeschehen, um neue Wege der Anleitung anzubahnen. Im Fokus stehen die Lehrpersonen, ihr Wirken und ihre im Prozess sich vollziehende Professionalisierung.
Die Studie gliedert sich in vier Teile. Der erste Teil legt die musikfachlichen und professionstheoretischen Fundierungen dar. Diese Fundierungen bilden die Grundlage vorliegender fachgegenstandsspezifischer Professionalisierung. Der zweite Teil stellt das Forschungsformat von Design-based Research sowie dessen konkrete Adaption vor. Der dritte Teil expliziert das empirische Vorgehen im Feld. Der vierte Teil berichtet die Ergebnisse in Form von Designprinzipien und Designprodukten.
Die leitende Forschungsfrage lautet:
Wie verläuft der Kompetenzerwerb von Klassenlehrpersonen auf der Primarstufe beim Anleiten musikalischer Gestaltungsprozesse und wie lässt sich dieser Kompetenzerwerb mittels Reflexionstools unterstützen?
Das Forschungsziel ist demnach ein doppeltes: Erstens Erkenntnisgewinnung zur Struktur des Kompetenzerwerbs im begleiteten Selbstlernprozess der Lehrer:innen. Zweitens die Generierung von Reflexionstools, die Klassenlehrpersonen bei der Initiierung und Moderation musikalischer Gestaltungsprozesse in der Praxis unterstützen.
Die Untersuchung nimmt eine offene Herausforderung aus der Bildungspraxis als Ausgangspunkt für fachspezifische Professionalisierung an. Das Forschungsformat von Design-based Research erwies sich als sinnvolle Strategie, da die Lehrkräfte ihre Professionalisierung als theoriegestützten Selbstlernprozess in ihrem angestammten Praxisfeld angehen konnten.
Die Auswertung der Befragungen, die im Rahmen der Designprozesse erfolgten, zeigt, dass die Untersuchungsteilnehmenden ihr sozial-kommunikatives Verhalten sowie ihre fachdidaktischen Zugänge und Vorgehensweisen veränderten und in Richtung einer didaktisch-improvisierenden Handlungsweise zu erweitern vermochten.
Am Ende der Untersuchung entstanden drei Reflexionstools in unterschiedlichen Formaten und auf unterschiedlichen Abstraktionsniveaus: Das Reflexionstool try-outs beinhaltet konkrete Reflexionsimpulse (Handlungsanregungen und Reflexionsfragen) für das unterrichtliche Lehrer:innen-Handeln. Das dynamische Kompetenzmodell Kompetenzflyer bietet eine Reflexionsfolie für die Ansteuerung eigenständiger Kompetenzerwerbsschritte. Das online-Tool improspider ist ein Selbstreflexionsinstrument zur Einschätzung personaler Orientierungen und bildet, auf Basis empirisch erarbeiteter Merkmale einer didaktisch-improvisierenden Handlungsweise beim Anleiten musikalischer Gestaltungsprozesse, Improvisationskompetenz individuell ab.
Strings of words can correspond to more than one interpretation or underlying structure, which makes them ambiguous. Prosody can be used to resolve this structural ambiguity. This dissertation investigates the use of prosodic cues in the domains of fundamental frequency (f0) and duration to disambiguate between two interpretations of ambiguous structures when speakers addressed different interlocutors. The dissertation comprises of three production studies and one comprehension study.
Prosodic disambiguation was studied with a focus on German name sequences of three names (coordinates) in two conditions: without (Name1 and Name2 and Name3) and with internal grouping of the first two names ([Name1 and Name2] and Name3). The study of coordinates was complemented with production data of locally ambiguous sentences with a case-ambiguous first noun phrase.
Variability was studied in a controlled setting: Productions were elicited with a within-subject manipulation of context in a referential communication task in order to evoke prosodic adaptations to different conversational contexts. Context had five levels and involved interlocutors in three age groups (child, young adult, elderly adult) with German as L1 in the absence of background white noise, the young adult with background white noise, and a young adult without German as L1. Variability was explored at different levels: within a group of young individuals (intra-group level), within and between young individuals (intra-individual level and inter-individual level, respectively), and comparing between the group of young and a group of older speakers (inter-group level).
Our data replicate the use of the three prosodic cues (f0-movement, final lengthening, and pause) in productions of young adult speakers and extend their use to productions of older adult speakers. Both age groups distinguished consistently between the two coordinate conditions. Prosodic grouping in production was evident not only on the group-final Name2 but also at earlier stages in the utterance, on the group-internal Name1 (early cues). For some speakers, some listeners were able to decode these early cues effectively as they were able to reliably predict the upcoming structure after listening to Name1 only. Thus, prosodic grouping appears as a globally marked phenomenon building up along the utterance. The internal structure of coordinates was disambiguated irrespective of the conversational context. In our data, speakers only slightly modified the prosodic cues marking the disambiguation in the different contexts. Listeners were unable to identify to which interlocutor the sequence had been produced. We interpret this intra-individual consistency in the production of disambiguating prosodic cues as support for a strong link between prosody and syntax. The findings support models in favour of situational independence of disambiguating prosody. All speakers reliably marked the distinction between the grouping conditions with at least one of the three prosodic cues investigated and most of the speakers used at least two of these cues. Further, individual differences in prosodic grouping did not lead to difficulties in recovering the grouping in comprehension. Taken together, these findings support the existence of a phonological category of prosodic grouping.
Characterization of the role of stress - responsive NAC transcription factors ANAC055 and ATAF1
(2022)
Starch is a biopolymer for which, despite its simple composition, understanding the precise mechanism behind its formation and regulation has been challenging. Several approaches and bioanalytical tools can be used to expand the knowledge on the different parts involved in the starch metabolism. In this sense, a comprehensive analysis targeting two of the main groups of molecules involved in this process: proteins, as effectors/regulators of the starch metabolism, and maltodextrins as starch components and degradation products, was conducted in this research work using potato plants (Solanum tuberosum L. cv. Desiree) as model of study. On one side, proteins physically interacting to potato starch were isolated and analyzed through mass spectrometry and western blot for their identification. Alternatively, starch interacting proteins were explored in potato tubers from transgenic plants having antisense inhibition of starch-related enzymes and on tubers stored under variable environmental conditions. Most of the proteins recovered from the starch granules corresponded to previously described proteins having a specific role in the starch metabolic pathway. Another set of proteins could be grouped as protease inhibitors, which were found weakly interacting to starch. Variations in the protein profile obtained after electrophoresis separation became clear when tubers were stored under different temperatures, indicating a differential expression of proteins in response to changing environmental conditions.
On the other side, since maltodextrin metabolism is thought to be involved in both starch initiation and degradation, soluble maltooligosaccharide content in potato tubers was analyzed in this work under diverse experimental variables. For this, tuber disc samples from wild type and transgenic lines strongly repressing either the plastidial or cytosolic form of the -glucan phosphorylase and phosphoglucomutase were incubated with glucose, glucose-6-phosphate, and glucose-1-phosphate solutions to evaluate the influence of such enzymes on the conversion of the carbon sources into soluble maltodextrins, in comparison to wild-type samples. Relative maltodextrin amounts analyzed through capillary electrophoresis equipped with laser-induced fluorescence (CE-LIF) revealed that tuber discs could immediately uptake glucose-1-phosphate and use it to produce maltooligosaccharides with a degree of polymerization of up to 30 (DP30), in contrast to transgenic tubers with strong repression of the plastidial glucan phosphorylase. The results obtained from the maltodextrin analysis support previous indications that a specific transporter for glucose-1-phosphate may exist in both the plant cells and the plastidial membranes, thereby allowing a glucose-6-phosphate independent transport. Furthermore, it confirms that the plastidial glucan phosphorylase is responsible for producing longer maltooligosaccharides in the plastids by catalyzing a glucan polymerization reaction when glucose-1-phosphate is available. All these findings contribute to a better understanding of the role of the plastidial glucan phosphorylase as a key enzyme directly involved in the synthesis and degradation of glucans and their implication on starch metabolism.
The deformation style of mountain belts is greatly influenced by the upper plate architecture created during preceding deformation phases. The Mesozoic Salta Rift extensional phase has created a dominant structural and lithological framework that controls Cenozoic deformation and exhumation patterns in the Central Andes. Studying the nature of these pre-existing anisotropies is a key to understanding the spatiotemporal distribution of exhumation and its controlling factors. The Eastern Cordillera in particular, has a structural grain that is in part controlled by Salta Rift structures and their orientation relative to Andean shortening. As a result, there are areas in which Andean deformation prevails and areas where the influence of the Salta Rift is the main control on deformation patterns.
Between 23 and 24°S, lithological and structural heterogeneities imposed by the Lomas de Olmedo sub-basin (Salta Rift basin) affect the development of the Eastern Cordillera fold-and-thrust belt. The inverted northern margin of the sub-basin now forms the southern boundary of the intermontane Cianzo basin. The former western margin of the sub-basin is located at the confluence of the Subandean Zone, the Santa Barbara System and the Eastern Cordillera. Here, the Salta Rift basin architecture is responsible for the distribution of these morphotectonic provinces. In this study we use a multi-method approach consisting of low-temperature (U-Th-Sm)/He and apatite fission track thermochronology, detrital geochronology, structural and sedimentological analyses to investigate the Mesozoic structural inheritance of the Lomas de Olmedo sub-basin and Cenozoic exhumation patterns.
Characterization of the extension-related Tacurú Group as an intermediate succession between Paleozoic basement and the syn-rift infill of the Lomas de Olmedo sub-basin reveals a Jurassic maximum depositional age. Zircon (U-Th-Sm)/He cooling ages record a pre-Cretaceous onset of exhumation for the rift shoulders in the northern part of the sub-basin, whereas the western shoulder shows a more recent onset (140–115 Ma). Variations in the sedimentary thickness of syn- and post-rift strata document the evolution of accommodation space in the sub-basin. While the thickness of syn-rift strata increases rapidly toward the northern basin margin, the post-rift strata thickness decreases toward the margin and forms a condensed section on the rift shoulder.
Inversion of Salta Rift structures commenced between the late Oligocene and Miocene (24–15 Ma) in the ranges surrounding the Cianzo basin. The eastern and western limbs of the Cianzo syncline, located in the hanging wall of the basin-bounding Hornocal fault, show diachronous exhumation. At the same time, western fault blocks of Tilcara Range, south of the Cianzo basin, began exhuming in the late Oligocene to early Miocene (26–16 Ma). Eastward propagation to the frontal thrust and to the Paleozoic strata east of the Tilcara Range occurred in the middle Miocene (22–10 Ma) and the late Miocene–early Pliocene (10–4 Ma), respectively.
Anschaulichkeiten herstellen
(2023)
Die Handschrift D der Driu liet von der maget entstand um 1220 und ist die älteste vollständige erhaltene Fassung des Textes. Priester Wernher gilt als Verfasser der geistlichen Dichtung und erstellt sie im Jahr 1172 auf der Grundlage apokrypher und biblischer Quellen. Die Handschrift D wird in der mediävistischen Germanistik gerne zu jenen Werken gezählt, die den Auftakt einer zunehmenden Verschriftlichung in der Volkssprache markieren. Gemäß ihrem Erscheinungsbild erweist sich die Handschrift und der Zeitpunkt ihrer Entstehung aber vor allem als ein Wendepunkt, an dem der Einfluss der lateinischen Schriftkultur auf die Produktion volkssprachlicher Literatur besonders deutlich wird. Während insgesamt der Anteil der geistlichen Dichtung kontinuierlich abnimmt, erfolgt von literaturwissenschaftlicher Seite zurecht auch die Einordnung der Handschrift in die weltlich-laikale Hofliteratur. In diesem Kontext steht die Handschrift D aber nicht am Beginn einer Blütezeit, sondern weist vor allem in das blühende Spannungsfeld zwischen der lateinisch geprägten Buchproduktion und der geistlichen Dichtung auf der einen und dem Anspruch einer laikalen Rezeptionsgemeinschaft auf der anderen Seite. In diesem Feld bewegt sich meine medienanthropologische Untersuchung. Die Schwerpunkte liegen hierbei auf der Rekonstruktion der Handschriftenherstellung sowie auf der Analyse der Darstellungsprinzipien im Bildprogramm.
Obwohl sieben der neun Menschenrechtsverträge auf Ebene der Vereinten Nationen die Möglichkeit eines Staatenbeschwerdeverfahrens eröffnen, kam dieser Verfahrensart über Jahrzehnte hinweg keinerlei praktische Bedeutung zu. Im Frühjahr 2018 erreichten den CERD-Ausschuss dann jedoch gleich drei verschiedene Staatenmitteilungen. Die erstmalige Aktivierung des Verfahrens fast 50 Jahre nach Inkrafttreten des Internationalen Übereinkommens zur Beseitigung jeder Form von Rassendiskriminierung (CERD) kann dabei als eine historische Entwicklung bezeichnet werden.
Vor diesem Hintergrund bietet dieses Buch erstmals eine umfassende Auseinandersetzung mit dem Staatenbeschwerdeverfahren nach Art. 11-13 CERD und den sich daraus ergebenden völkerrechtlichen Fragen. Unter Auswertung der jüngsten Praxis des CERD-Ausschusses und der ad hoc Vergleichskommission wird die Funktionsweise des Verfahrens detailliert dargestellt, wobei immer wieder Parallelen zu den Mechanismen anderer Vertragsregime gezogen werden. Auf diese Weise soll die Arbeit auch zu dem Verständnis vergleichbarer Staatenbeschwerdeverfahren anderer Menschenrechtsverträge beitragen und zugleich die Bedeutung des Phänomens zwischenstaatlicher Streitbeilegung in Menschenrechtsfragen stärker in den Vordergrund rücken.
Background and aims:
To succeed in competition, elite team and individual athletes often seek the development of both, high levels of muscle strength and power as well as cardiorespiratory endurance. In this context, concurrent training (CT) is a commonly applied and effective training approach. While being exposed to high training loads, youth athletes (≤ 18 years) are yet underrepresented in the scientific literature. Besides, immunological responses to CT have received little attention. Therefore, the aims of this work were to examine the acute (< 15min) and delayed (≥ 6 hours) effects of dif-ferent exercise order in CT on immunological stress responses, muscular fitness, metabolic response, and rating of perceived exertion (RPE) in highly trained youth male and female judo athletes.
Methods:
A total of twenty male and thirteen female participants, with an average age of 16 ± 1.8 years and 14.4 ± 2.1 years, respectively, were included in the study. They were randomly assigned to two CT sessions; power-endurance versus endurance-power (i.e., study 1), or strength-endurance versus endurance-strength (i.e., study 2). Markers of immune response (i.e., white-blood-cells, granulocytes, lymphocytes, mon-ocytes, and lymphocytes, granulocyte-lymphocyte-ratio, and systemic-inflammation-index), muscular fitness (i.e., counter-movement jump [CMJ]), metabolic responses (i.e., blood lactate, glucose), and RPE were collected at different time points (i.e., PRE12H, PRE, MID, POST, POST6H, POST22H).
Results (study 1):
There were significant time*order interactions for white-blood-cells, lymphocytes, granulocytes, monocytes, granulocyte-lymphocyte-ratio, and systemic-inflammation-index. The power-endurance order resulted in significantly larger PRE-to-POST increases in white-blood-cells, monocytes, and lymphocytes while the endur-ance-power order resulted in significantly larger PRE-to-POST increases in the granu-locyte-lymphocyte-ratio and systemic-inflammation-index. Likewise, significantly larger increases from PRE-to-POST6H in white-blood-cells and granulocytes were observed following the power-endurance order compared to endurance-power. All markers of immune response returned toward baseline values at POST22H. Moreover, there was a significant time*order interaction for blood glucose and lactate. Following the endur-ance-power order, blood lactate and glucose increased from PRE-to-MID but not from PRE-to-POST. Meanwhile, in the power-endurance order blood lactate and glucose increased from PRE-to-POST but not from PRE-to-MID. A significant time*order inter-action was observed for CMJ-force with larger PRE-to-POST decreases in the endur-ance-power order compared to power-endurance order. Further, CMJ-power showed larger PRE-to-MID performance decreases following the power-endurance order, com-pared to the endurance-power order. Regarding RPE, significant time*order interactions were noted with larger PRE-to-MID values following the endurance-power order and larger PRE-to-POST values following the power-endurance order.
Results (study 2):
There were significant time*order interactions for lymphocytes, monocytes, granulocyte-lymphocyte-ratio, and systemic-inflammation-index. The strength-endurance order resulted in significantly larger PRE-to-POST increases in lymphocytes while the endurance-strength order resulted in significantly larger PRE-to-POST increases in the granulocyte-lymphocyte-ratio and systemic-inflammation-index. All markers of the immune system returned toward baseline values at POST22H. Moreover, there was a significant time*order interaction for blood glucose and lactate. From PRE-to-MID, there was a significantly greater increase in blood lactate and glu-cose following the endurance-strength order compared to strength-endurance order. Meanwhile, from PRE-to-POST there was a significantly higher increase in blood glu-cose following the strength-endurance order compared to endurance-strength order. Regarding physical fitness, a significant time*order interaction was observed for CMJ-force and CMJ-power with larger PRE-to-MID increases following the endurance-strength order compared to the strength-endurance order. For RPE, significant time*order interactions were noted with larger PRE-to-MID values following the endur-ance-power order and larger PRE-to-POST values following the power-endurance or-der.
Conclusions:
The primary findings from both studies revealed order-dependent effects on immune responses. In male youth judo athletes, the results demonstrated greater immunological stress responses, both immediately (≤ 15 min) and delayed (≥ 6 hours), following the power-endurance order compared to the endurance-power order. For female youth judo athletes, the results indicated higher acute, but not delayed, order-dependent changes in immune responses following the strength-endurance order compared to the endurance-strength order. It is worth noting that in both studies, all markers of immune system response returned to baseline levels within 22 hours. This suggests that successful recovery from the exercise-induced immune stress response was achieved within 22 hours. Regarding metabolic responses, physical fitness, and perceived exertion, the findings from both studies indicated acute (≤ 15 minutes) alterations that were dependent on the exercise order. These alterations were primarily influ-enced by the endurance exercise component. Moreover, study 1 provided substantial evidence suggesting that internal load measures, such as immune markers, may differ from external load measures. This indicates a disparity between immunological, perceived, and physical responses following both concurrent training orders. Therefore, it is crucial for practitioners to acknowledge these differences and take them into consideration when designing training programs.
BCH Codes mit kombinierter Korrektur und Erkennung In dieser Arbeit wird auf Grundlage des BCH Codes untersucht, wie eine Fehlerkorrektur mit einer Erkennung höherer Fehleranzahlen kombiniert werden kann. Mit dem Verfahren der 1-Bit Korrektur mit zusätzlicher Erkennung höherer Fehler wurde ein Ansatz entwickelt, welcher die Erkennung zusätzlicher Fehler durch das parallele Lösen einfacher Gleichungen der Form s_x = s_1^x durchführt. Die Anzahl dieser Gleichungen ist linear zu der Anzahl der zu überprüfenden höheren Fehler.
In dieser Arbeit wurde zusätzlich für bis zu 4-Bit Korrekturen mit zusätzlicher Erkennung höherer Fehler ein weiterer allgemeiner Ansatz vorgestellt. Dabei werden parallel für alle korrigierbaren Fehleranzahlen spekulative Fehlerkorrekturen durchgeführt. Aus den bestimmten Fehlerstellen werden spekulative Syndromkomponenten erzeugt, durch welche die Fehlerstellen bestätigt und höhere erkennbare Fehleranzahlen ausgeschlossen werden können. Die vorgestellten Ansätze unterscheiden sich von dem in entwickelten Ansatz, bei welchem die Anzahl der Fehlerstellen durch die Berechnung von Determinanten in absteigender Reihenfolge berechnet wird, bis die erste Determinante 0 bildet. Bei dem bekannten Verfahren ist durch die Berechnung der Determinanten eine faktorielle Anzahl an Berechnungen in Relation zu der Anzahl zu überprüfender Fehler durchzuführen. Im Vergleich zu dem bekannten sequentiellen Verfahrens nach Berlekamp Massey besitzen die Berechnungen im vorgestellten Ansatz simple Gleichungen und können parallel durchgeführt werden.Bei dem bekannten Verfahren zur parallelen Korrektur von 4-Bit Fehlern ist eine Gleichung vierten Grades im GF(2^m) zu lösen. Dies erfolgt, indem eine Hilfsgleichung dritten Grades und vier Gleichungen zweiten Grades parallel gelöst werden. In der vorliegenden Arbeit wurde gezeigt, dass sich eine Gleichung zweiten Grades einsparen lässt, wodurch sich eine Vereinfachung der Hardware bei einer parallelen Realisierung der 4-Bit Korrektur ergibt. Die erzielten Ergebnisse wurden durch umfangreiche Simulationen in Software und Hardwareimplementierungen überprüft.
The present work focuses on the preparation and characterisation of various nanoplastic reference material candidates. Nanoplastics are plastic particles in a size range of 1 − 1000 nm. The term has emerged in recent years as a distinction from the larger microplastic (1 − 1000 μm). Since the properties of the two plastic particles differ significantly due to their size, it is important to have nanoplastic reference material. This was produced for the polymer types polypropylene (PP) and polyethylene (PE) as well as poly(lactic acid) (PLA).
A top-down method was used to produce the nanoplastic for the polyolefins PP and PE (Section 3.1). The material was crushed in acetone using an Ultra-Turrax disperser and then transferred to water. This process produces reproducible results when repeated, making it suitable for the production of a reference material candidate. The resulting dispersions were investigated using dynamic and electrophoretic light scattering. The dispersion of PP particles gave a mean hydrodynamic diameter Dh = 180.5±5.8 nm with a PDI = 0.08±0.02 and a zeta potential ζ = −43.0 ± 2.0 mV. For the PE particles, a diameter Dh = 344.5 ± 34.6 nm, with a PDI = 0.39 ± 0.04 and a zeta potential of ζ = −40.0 ± 4.2 mV was measured. This means that both dispersions are nanoplastics, as the particles are < 1000 nm. Furthermore, the starting material of these polyolefin particles was mixed with a gold salt and thereby the nanoplastic production was repeated in order to obtain nanoplastic particles doped with gold, which should simplify the detection of the particles.
In addition to the top-down approach, a bottom-up method was chosen for the PLA (Section 3.2). Here, the polymer was first dissolved in THF and stabilised with a surfactant. Then water was added and THF evaporated, leaving an aqueous PLA dispersion. This experiment was also investigated using dynamic light scattering and, when repeated, yielded reproducible results, i. e. an average hydrodynamic diameter of Dh = 89.2 ± 3.0 nm. Since the mass concentration of PLA in the dispersion is known due to the production method, a Python notebook was tested for these samples to calculate the number and mass concentration of nano(plastic) particles using the MALS results. Similar to the plastic produced in Section 3.1, gold was also incorporated into the particle, which was achieved by adding a dispersion of gold clusters with a diameter of D = 1.15 nm in an ionic liquid (IL) in the production process. Here, the preparation of the gold clusters in the ionic liquid 1-ethyl-3-methylimidazolium dicyanamide ([Emim][DCA]) represented the first use of an IL both as a reducing agent for gold and as a solvent for the gold clusters. Two volumes of gold cluster dispersion were added during the PLA particle synthesis. The addition of the gold clusters leads to much larger particles. The nanoPLA with 0.8% Au has a diameter of Dh = 198.0 ± 10.8 nm and the nanoPLA with 4.9% Au has a diameter of Dh = 259.1 ± 23.7 nm. First investigations by TEM imaging show that the nanoPLA particles form hollow spheres when gold clusters are added. However, the mechanism leading to these structures remains unclear.
In the present thesis, AC electrokinetic forces, like dielectrophoresis and AC electroosmosis, were demonstrated as a simple and fast method to functionalize the surface of nanoelectrodes with submicrometer sized biological objects. These nanoelectrodes have a cylindrical shape with a diameter of 500 nm arranged in an array of 6256 electrodes. Due to its medical relevance influenza virus as well as anti-influenza antibodies were chosen as a model organism. Common methods to bring antibodies or proteins to biosensor surfaces are complex and time-consuming. In the present work, it was demonstrated that by applying AC electric fields influenza viruses and antibodies can be immobilized onto the nanoelectrodes within seconds without any prior chemical modification of neither the surface nor the immobilized biological object. The distribution of these immobilized objects is not uniform over the entire array, it exhibits a decreasing gradient from the outer row to the inner ones. Different causes for this gradient have been discussed, such as the vortex-shaped fluid motion above the nanoelectrodes generated by, among others, electrothermal fluid flow. It was demonstrated that parts of the accumulated material are permanently immobilized to the electrodes. This is a unique characteristic of the presented system since in the literature the AC electrokinetic immobilization is almost entirely presented as a method just for temporary immobilization. The spatial distribution of the immobilized viral material or the anti-influenza antibodies at the electrodes was observed by either the combination of fluorescence microscopy and deconvolution or by super-resolution microscopy (STED). On-chip immunoassays were performed to examine the suitability of the functionalized electrodes as a potential affinity-based biosensor. Two approaches were pursued: A) the influenza virus as the bio-receptor or B) the influenza virus as the analyte. Different sources of error were eliminated by ELISA and passivation experiments. Hence, the activity of the immobilized object was inspected by incubation with the analyte. This resulted in the successful detection of anti-influenza antibodies by the immobilized viral material. On the other hand, a detection of influenza virus particles by the immobilized anti-influenza antibodies was not possible. The latter might be due to lost activity or wrong orientation of the antibodies. Thus, further examinations on the activity of by AC electric fields immobilized antibodies should follow. When combined with microfluidics and an electrical read-out system, the functionalized chips possess the potential to serve as a rapid, portable, and cost-effective point-of-care (POC) device. This device can be utilized as a basis for diverse applications in diagnosing and treating influenza, as well as various other pathogens.
Stars under influence: evidence of tidal interactions between stars and substellar companions
(2023)
Tidal interactions occur between gravitationally bound astrophysical bodies. If their spatial separation is sufficiently small, the bodies can induce tides on each other, leading to angular momentum transfer and altering of evolutionary path the bodies would have followed if they were single objects. The tidal processes are well established in the Solar planet-moon systems and close stellar binary systems. However, how do stars behave if they are orbited by a substellar companion (e.g. a planet or a brown dwarf) on a tight orbit?
Typically, a substellar companion inside the corotation radius of a star will migrate toward the star as it loses orbital angular momentum. On the other hand, the star will gain angular momentum which has the potential to increase its rotation rate. The effect should be more pronounced if the substellar companion is more massive. As the stellar rotation rate and the magnetic activity level are coupled, the star should appear more magnetically active under the tidal influence of the orbiting substellar companion. However, the difficulty in proving that a star has a higher magnetic activity level due to tidal interactions lies in the fact that (I) substellar companions around active stars are easier to detect if they are more massive, leading to a bias toward massive companions around active stars and mimicking the tidal interaction effect, and that (II) the age of a main-sequence star cannot be easily determined, leaving the possibility that a star is more active due to its young age.
In our work, we overcome these issues by employing wide stellar binary systems where one star hosts a substellar companion, and where the other star provides the magnetic activity baseline for the host star, assuming they have coevolved, and thereby provides the host's activity level if tidal interactions have no effect on it. Firstly, we find that extrasolar planets can noticeably increase the host star's X-ray luminosity and that the effect is more pronounced if the exoplanet is at least Jupiter-like in mass and close to the star. Further, we find that a brown dwarf will have an even stronger effect, as expected, and that the X-ray surface flux difference between the host star and the wide stellar companion is a significant outlier when compared to a large sample of similar wide binary systems without any known substellar companions. This result proves that substellar hosting wide binary systems can be good tools to reveal the tidal effect on host stars, and also show that the typical stellar age indicators as activity or rotation cannot be used for these stars. Finally, knowing that the activity difference is a good tracer of the substellar companion's tidal impact, we develop an analytical method to calculate the modified tidal quality factor Q' of individual host stars, which defines the tidal dissipation efficiency in the convective envelope of a given main-sequence star.
This dissertation focuses on the understanding of the optical manipulation of microgels dispersed in aqueous solution of azobenzene containing surfactant. The work consists of three parts where each part is a systematic investigation of the (1) photo-isomerization kinetics of the surfactant in complex with the microgel polymer matrix, (2) light driven diffusiosmosis (LDDO) in microgels and (3) photo-responsivity of microgel on complexation with spiropyran.
The first part comprises three publications where the first one [P1] investigates the photo-isomerization kinetics and corresponding isomer composition at a photo-stationary state of the photo-sensitive surfactant conjugated with charged polymers or micro sized polymer networks to understand the structural response of such photo-sensitive complexes. We report that the photo-isomerization of the azobenzene-containing cationic surfactant is slower in a polymer complex compared to being purely dissolved in an aqueous solution. The surfactant aggregates near the polyelectrolyte chains at concentrations much lower than the bulk critical micelle concentration. This, along with the inhibition of the photo-isomerization kinetics due to steric hindrance within the densely packed aggregates, pushes the isomer-ratio to a higher trans-isomer concentration for all irradiation wavelengths.
The second publication [P2] combines experimental results and non-adiabatic dynamic simulations for the same surfactant molecules embedded in the micelles with absorption spectroscopy measurements of micellar solutions to uncover the reasons responsible for the slowdown in photo induced trans → cis azobenzene isomerization at concentrations higher than the critical micelle concentration (CMC). The simulations reveal a decrease of isomerization quantum yields for molecules inside the micelles and observes a reduction of extinction coefficients upon micellization. These findings explain the deceleration of the trans → cis switching in micelles of the azobenzene-containing surfactants.
Finally, the third publication [P3] focusses on the kinetics of adsorption and desorption of the same surfactant within anionic microgels in the dark and under continuous irradiation. Experimental data demonstrate, that microgels can serve as a selective absorber of the trans isomers. The interaction of the isomers with the gel matrix induces a remotely controllable collapse or swelling on appropriate irradiation wavelengths. Measuring the kinetics of the microgel size response and knowing the exact isomer composition under light exposure, we calculate the adsorption rate of the trans-isomers.
The second part comprises two publications. The first publication [P4] reports on the phenomenon of light-driven diffusioosmotic (DO) long-range attractive and repulsive interactions between micro-sized objects, whose range extends several times the size of microparticles and can be adjusted to point towards or away from the particle by varying irradiation parameters such as intensity or wavelength of light. The phenomenon is fueled by the aforementioned photosensitive surfactant. The complex interaction of dynamic exchange of isomers and photo-isomerization rate yields to relative concentrations gradients of the isomers in the vicinity of micro-sized object inducing a local diffusioosmotic (DO) flow thereby making a surface act as a micropump.
The second publication [P5] exclusively aims the visualization and investigation of the DO flows generated from microgels by using small tracer particles. Similar to micro sized objects, the flow is able to push adjacent tracers over distances several times larger than microgel size. Here we report that the direction and the strength of the l-LDDO depends on the intensity, irradiation wavelength and the amount of surfactant adsorbed by the microgel. For example, the flow pattern around a microgel is directed radially outward and can be maintained quasi-indefinitely under exposure at 455 nm when the trans:cis ratio is 2:1, whereas irradiation at 365 nm, generates a radially transient flow pattern, which inverts at lower intensities.
Lastly, the third part consists of one publication [P6] which, unlike the previous works, reports on the study of the kinetics of photo- and thermo-switching of a new surfactant namely, spiropyran, upon exposure with light of different wavelengths and its interaction with p(NIPAM-AA) microgels. The surfactant being an amphiphile, switches between its ring closed spiropyran (SP) form and ring open merocyanine (MC) form which results in a change in the hydrophilic–hydrophobic balance of the surfactant as MC being a zwitterionic form along with the charged head group, generates three charges on the molecule. Therefore, the MC form of the surfactant is more hydrophilic than in the case of the neutral SP state. Here, we investigate the initial shrinkage of the gel particles via charge compensation on first exposure to SP molecules which results from the complex formation of the molecules with the gel matrix, triggering them to become photo responsive. The size and VPTT of the microgels during irradiation is shown to be a combination of heating up of the solution during light absorption by the surfactant (more pronounced in the case of UV irradiation) and the change in the hydrophobicity of the surfactant.
Point processes are a common methodology to model sets of events. From earthquakes to social media posts, from the arrival times of neuronal spikes to the timing of crimes, from stock prices to disease spreading -- these phenomena can be reduced to the occurrences of events concentrated in points. Often, these events happen one after the other defining a time--series.
Models of point processes can be used to deepen our understanding of such events and for classification and prediction. Such models include an underlying random process that generates the events. This work uses Bayesian methodology to infer the underlying generative process from observed data. Our contribution is twofold -- we develop new models and new inference methods for these processes.
We propose a model that extends the family of point processes where the occurrence of an event depends on the previous events. This family is known as Hawkes processes. Whereas in most existing models of such processes, past events are assumed to have only an excitatory effect on future events, we focus on the newly developed nonlinear Hawkes process, where past events could have excitatory and inhibitory effects. After defining the model, we present its inference method and apply it to data from different fields, among others, to neuronal activity.
The second model described in the thesis concerns a specific instance of point processes --- the decision process underlying human gaze control. This process results in a series of fixated locations in an image. We developed a new model to describe this process, motivated by the known Exploration--Exploitation dilemma. Alongside the model, we present a Bayesian inference algorithm to infer the model parameters.
Remaining in the realm of human scene viewing, we identify the lack of best practices for Bayesian inference in this field. We survey four popular algorithms and compare their performances for parameter inference in two scan path models.
The novel models and inference algorithms presented in this dissertation enrich the understanding of point process data and allow us to uncover meaningful insights.
Traditionally, mental disorders have been identified based on specific symptoms and standardized diagnostic systems such as the DSM-5 and ICD-10. However, these symptom-based definitions may only partially represent neurobiological and behavioral research findings, which could impede the development of targeted treatments. A transdiagnostic approach to mental health research, such as the Research Domain Criteria (RDoC) approach, maps resilience and broader aspects of mental health to associated components. By investigating mental disorders in a transnosological way, we can better understand disease patterns and their distinguishing and common factors, leading to more precise prevention and treatment options.
Therefore, this dissertation focuses on (1) the latent domain structure of the RDoC approach in a transnosological sample including healthy controls, (2) its domain associations to disease severity in patients with anxiety and depressive disorders, and (3) an overview of the scientific results found regarding Positive (PVS) and Negative Valence Systems (NVS) associated with mood and anxiety disorders.
The following main results were found: First, the latent RDoC domain structure for PVS and NVS, Cognitive Systems (CS), and Social Processes (SP) could be validated using self-report and behavioral measures in a transnosological sample. Second, we found transdiagnostic and disease-specific associations between those four domains and disease severity in patients with depressive and anxiety disorders. Third, the scoping review showed a sizable amount of RDoC research conducted on PVS and NVS in mood and anxiety disorders, with research gaps for both domains and specific conditions.
In conclusion, the research presented in this dissertation highlights the potential of the transnosological RDoC framework approach in improving our understanding of mental disorders. By exploring the latent RDoC structure and associations with disease severity and disease-specific and transnosological associations for anxiety and depressive disorders, this research provides valuable insights into the full spectrum of psychological functioning. Additionally, this dissertation highlights the need for further research in this area, identifying both RDoC indicators and research gaps. Overall, this dissertation represents an important contribution to the ongoing efforts to improve our understanding and the treatment of mental disorders, particularly within the commonly comorbid disease spectrum of mood and anxiety disorders.
Dielektrophorese ist die Manipulation polarisierbarer Partikel durch inhomogene elektrische Wechselfelder. In dieser Arbeit wurden drei verschiedene Enzyme durch Dielektrophorese immobilisiert und anschließend hinsichtlich ihrer katalytischen Aktivität untersucht: Meerrettichperoxidase, Cholinoxidase aus Alcaligenes sp. und Glucoseoxidase aus Aspergillus niger. Die Immobilisierung erfolgte durch Dielektrophorese auf nano-Elektrodenarrays aus Wolfram-Zylindern mit 500 nm Durchmesser oder aus Titannitrid-Ringen mit 20 nm Breite. Die Immobilisierung der Enzyme konnte fluoreszenzmikroskopisch entweder anhand der intrinsischen Fluoreszenz oder aufgrund einer Fluoreszenzmarkierung vor oder nach der Immobilisierung für alle getesteten Enzyme nachgewiesen werden. Die Messung der Enzymaktivität erfolgte quantitativ durch den direkten oder indirekten Nachweis des gebildeten Produktes oder, im Falle der Cholinoxidase, durch Beobachtung der intrinsischen Fluoreszenz des Cofaktors FAD, die vom Oxidationszustand dieses Enzyms abhängt. Für die Meerrettichperoxidase konnte so eine hohe erhaltene Enzymaktivität nach der Immobilisierung nachgewiesen werden. Die Aktivität der permanent immobilisierten Fraktion der Meerrettichperoxidase entsprach bis zu 47 % der höchstmöglichen Aktivität einer Monolage dieses Enzyms auf den Elektroden des Chips. Diese Aktivität kann als aktive, aber zufällig gegenüber der Oberfläche ausgerichtete Enzymschicht interpretiert werden. Für die permanent immobilisierte Glucoseoxidase wurde nur eine Aktivität entsprechend <1,3 % der Aktivität einer solchen Enzymschicht detektiert, während für die immobilisierte Cholinoxidase gar keine Aktivität nachgewiesen werden konnte. Die Aktivität der durch DEP immobilisierten Enzyme konnte somit quantitativ bestimmt werden. Der Anteil an erhaltener Aktivität hängt dabei stark vom verwendeten Enzym ab.
Digitalisation in industry – also called “Industry 4.0” – is seen by numerous actors as an opportunity to reduce the environmental impact of the industrial sector. The scientific assessments of the effects of digitalisation in industry on environmental sustainability, however, are ambivalent. This cumulative dissertation uses three empirical studies to examine the expected and observed effects of digitalisation in industry on environmental sustainability. The aim of this dissertation is to identify opportunities and risks of digitalisation at different system levels and to derive options for action in politics and industry for a more sustainable design of digitalisation in industry. I use an interdisciplinary, socio-technical approach and look at selected countries of the Global South (Study 1) and the example of China (all studies). In the first study (section 2, joint work with Marcel Matthess), I use qualitative content analysis to examine digital and industrial policies from seven different countries in Africa and Asia for expectations regarding the impact of digitalisation on sustainability and compare these with the potentials of digitalisation for sustainability in the respective country contexts. The analysis reveals that the documents express a wide range of vague expectations that relate more to positive indirect impacts of information and communication technology (ICT) use, such as improved energy efficiency and resource management, and less to negative direct impacts of ICT, such as electricity consumption through ICT. In the second study (section 3, joint work with Marcel Matthess, Grischa Beier and Bing Xue), I conduct and analyse interviews with 18 industry representatives of the electronics industry from Europe, Japan and China on digitalisation measures in supply chains using qualitative content analysis. I find that while there are positive expectations regarding the effects of digital technologies on supply chain sustainability, their actual use and observable effects are still limited. Interview partners can only provide few examples from their own companies which show that sustainability goals have already been pursued through digitalisation of the supply chain or where sustainability effects, such as resource savings, have been demonstrably achieved. In the third study (section 4, joint work with Peter Neuhäusler, Melissa Dachrodt and Marcel Matthess), I conduct an econometric panel data analysis. I examine the relationship between the degree of Industry 4.0, energy consumption and energy intensity in ten manufacturing sectors in China between 2006 and 2019. The results suggest that overall, there is no significant relationship between the degree of Industry 4.0 and energy consumption or energy intensity in manufacturing sectors in China. However, differences can be found in subgroups of sectors. I find a negative correlation of Industry 4.0 and energy intensity in highly digitalised sectors, indicating an efficiency-enhancing effect of Industry 4.0 in these sectors. On the other hand, there is a positive correlation of Industry 4.0 and energy consumption for sectors with low energy consumption, which could be explained by the fact that digitalisation, such as the automation of previously mainly labour-intensive sectors, requires energy and also induces growth effects. In the discussion section (section 6) of this dissertation, I use the classification scheme of the three levels macro, meso and micro, as well as of direct and indirect environmental effects to classify the empirical observations into opportunities and risks, for example, with regard to the probability of rebound effects of digitalisation at the three levels. I link the investigated actor perspectives (policy makers, industry representatives), statistical data and additional literature across the system levels and consider political economy aspects to suggest fields of action for more sustainable (digitalised) industries. The dissertation thus makes two overarching contributions to the academic and societal discourse. First, my three empirical studies expand the limited state of research at the interface between digitalisation in industry and sustainability, especially by considering selected countries in the Global South and the example of China. Secondly, exploring the topic through data and methods from different disciplinary contexts and taking a socio-technical point of view, enables an analysis of (path) dependencies, uncertainties, and interactions in the socio-technical system across different system levels, which have often not been sufficiently considered in previous studies. The dissertation thus aims to create a scientifically and practically relevant knowledge basis for a value-guided, sustainability-oriented design of digitalisation in industry.
Functional characterization of ROS-responsive genes, ANAC085 and ATR7, in Arabidopsis thaliana
(2023)
Individuals with aphasia vary in the speed and accuracy they perform sentence comprehension tasks. Previous results indicate that the performance patterns of individuals with aphasia vary between tasks (e.g., Caplan, DeDe, & Michaud, 2006; Caplan, Michaud, & Hufford, 2013a). Similarly, it has been found that the comprehension performance of individuals with aphasia varies between homogeneous test sentences within and between sessions (e.g., McNeil, Hageman, & Matthews, 2005). These studies ascribed the variability in the performance of individuals with aphasia to random noise. This conclusion would be in line with an influential theory on sentence comprehension in aphasia, the resource reduction hypothesis (Caplan, 2012). However, previous studies did not directly compare variability in language-impaired and language-unimpaired adults. Thus, it is still unclear how the variability in sentence comprehension differs between individuals with and without aphasia. Furthermore, the previous studies were exclusively carried out in English. Therefore, the findings on variability in sentence processing in English still need to be replicated in a different language.
This dissertation aims to give a systematic overview of the patterns of variability in sentence comprehension performance in aphasia in German and, based on this overview, to put the resource reduction hypothesis to the test. In order to reach the first aim, variability was considered on three different dimensions (persons, measures, and occasions) following the classification by Hultsch, Strauss, Hunter, and MacDonald (2011). At the dimension of persons, the thesis compared the performance of individuals with aphasia and language-unimpaired adults. At the dimension of measures, this work explored the performance across different sentence comprehension tasks (object manipulation, sentence-picture matching). Finally, at the dimension of occasions, this work compared the performance in each task between two test sessions. Several methods were combined to study variability to gain a large and diverse database. In addition to the offline comprehension tasks, the self-paced-listening paradigm and the visual world eye-tracking paradigm were used in this work.
The findings are in line with the previous results. As in the previous studies, variability in sentence comprehension in individuals with aphasia emerged between test sessions and between tasks. Additionally, it was possible to characterize the variability further using hierarchical Bayesian models. For individuals with aphasia, it was shown that both between-task and between-session variability are unsystematic. In contrast to that, language-unimpaired individuals exhibited systematic differences between measures and between sessions. However, these systematic differences occurred only in the offline tasks. Hence, variability in sentence comprehension differed between language-impaired and language-unimpaired adults, and this difference could be narrowed down to the offline measures.
Based on this overview of the patterns of variability, the resource reduction hypothesis was evaluated. According to the hypothesis, the variability in the performance of individuals with aphasia can be ascribed to random fluctuations in the resources available for sentence processing. Given that the performance of the individuals with aphasia varied unsystematically, the results support the resource reduction hypothesis. Furthermore, the thesis proposes that the differences in variability between language-impaired and language-unimpaired adults can also be explained by the resource reduction hypothesis. More specifically, it is suggested that the systematic changes in the performance of language-unimpaired adults are due to decreasing fluctuations in available processing resources. In parallel, the unsystematic variability in the performance of individuals with aphasia could be due to constant fluctuations in available processing resources. In conclusion, the systematic investigation of variability contributes to a better understanding of language processing in aphasia and thus enriches aphasia research.
The emerging threat of antibiotic-resistant bacteria has become a global challenge in the last decades, leading to a rising demand for alternative treatments for bacterial infections. One approach is to target the bacterial cell envelope, making understanding its biophysical properties crucial. Specifically, bacteriophages use the bacterial envelope as an entry point to initiate infection, and they are considered important building blocks of new antibiotic strategies against drug-resistant bacteria.. Depending on the structure of the cell wall, bacteria are classified as Gram-negative and Gram-positive. Gram-negative bacteria are equipped with a complex cell envelope composed of two lipid membranes enclosing a rigid peptidoglycan layer. The synthesis machinery of the Gram-negative cell envelope is the target of antimicrobial agents, including new physical sanitizing procedures addressing the outer membrane (OM). It is therefore very important to study the biophysical properties of the Gram-negative bacterial cell envelope. The high complexity of the Gram-negative OM sets the demand for a model system in which the contribution of individual components can be evaluated separately. In this respect, giant unilamellar vesicles (GUVs) are promising membrane systems to study membrane properties while controlling parameters such as membrane composition and surrounding medium conditions.
The aim of this work was to develop methods and approaches for the preparation and characterization of a GUV-based membrane model that mimics the OM of the Gram-negative cell envelope. A major component of the OM is the lipopolysaccharide (LPS) on the outside of the OM heterobilayer. The vesicle model was designed to contain LPS in the outer leaflet and lipids in the inner leaflet. Furthermore, the interaction of the prepared LPS-GUVs with bacteriophages was tested. LPS containing GUVs were prepared by adapting the inverted emulsion technique to meet the challenging properties of LPS, namely their high self-aggregation rate in aqueous solutions. Notably, an additional emulsification step together with the adaption of solution conditions was employed to asymmetrically incorporate LPS containing long polysaccharide chains into the artificial membranes. GUV membrane asymmetry was verified with a fluorescence quenching assay. Since the necessary precautions for handling the quenching agent sodium dithionite are often underestimated and poorly described, important parameters were tested and identified to obtain a stable and reproducible assay. In the context of varied LPS incorporation, a microscopy-based technique was introduced to determine the LPS content on individual GUVs and to directly compare vesicle properties and LPS coverage. Diffusion coefficient measurements in the obtained GUVs showed that increasing LPS concentrations in the membranes resulted in decreased diffusivity.
Employing LPS-GUVs we could demonstrate that a Salmonella bacteriophage bound with high specificity to its LPS receptor when presented at the GUV surface, and that the number of bound bacteriophages scaled with the amount of presented LPS receptor. In addition to binding, the bacteriophages were able to eject their DNA into the vesicle lumen. LPS-GUVs thus provide a starting platform for bottom-up approaches for the generation of more complex membranes, in which the effects of individual components on the membrane properties and the interaction with antimicrobial agents such as bacteriophages could be explored.
Rechtschreibkompetenz ist eine wesentliche Voraussetzung, um eigenständig Texte verfassen zu können und somit am gesellschaftlichen Leben teilhaben zu können. Die vorliegende Arbeit nimmt daher die Rechtschreibkompetenz von Kindern der Grundschule genauer in den Blick. Mit Hilfe von drei empirischen Untersuchungen wird die Entwicklung der Rechtschreibkompetenz vor allem dahingehend betrachtet, inwiefern sich diese entlang von theoretischen Kompetenzmodellen entwickelt und welche Merkmale diese Entwicklung unterstützen können. Als Datengrundlage dient hierfür das Pilotprojekt inklusive Grundschule, in dem die Rechtschreibkompetenz von 697 Schülerinnen und Schülern zu insgesamt drei Messzeitpunkten (vom Beginn der zweiten Jahrgangsstufe bis zum Ende der dritten Jahrgangsstufe) untersucht wurde.
Mithilfe von latenten Transitionsanalysen konnte gezeigt werden, dass sich hinsichtlich des Ablaufs der Rechtschreibkompetenzniveaus nur sehr wenige Einzelfälle von den theoretischen Modellen unterscheiden. Anschließend zeigte sich durch multinomiale logistische Regressionen, dass Wechsel zwischen Kompetenzniveaus vor allem mit dem Arbeitsverhalten zusammenhingen, wohingegen hinsichtlich der Merkmale der Unterrichtsqualität nicht die erwarteten Zusammenhänge gezeigt werden konnten. Mögliche Ursachen und Implikationen werden in der Arbeit diskutiert.
Aptamers are single-stranded DNA (ssDNA) or RNA molecules that can bind specifically and with high affinity to target molecules due to their unique three-dimensional structure. For this reason, they are often compared to antibodies and sometimes even referred to as “chemical antibodies”. They are simple and inexpensive to synthesize, easy to modify, and smaller than conventional antibodies. Enzymes, especially hydrolases, are interesting targets in this context. This class of enzymes is capable of hydrolytically cleaving various macromolecules such as proteins, as well as smaller molecules such as antibiotics. Hence, they play an important role in many biological processes including diseases and their treatment. Hydrolase detection as well as the understanding of their function is therefore of great importance for diagnostics and therapy. Due to their various desirable features compared to antibodies, aptamers are being discussed as alternative agents for analytical and diagnostic use in various applications. The use of aptamers in therapy is also frequently investigated, as the binding of aptamers can have effects on the catalytic activity, protein-protein interactions, or proteolytic cascades. Aptamers are generated by an in vitro selection process. Potential aptamer candidates are selected from a pool of enriched nucleic acid sequences with affinity to the target, and their binding affinity and specificity is investigated. This is one of the most important steps in aptamer generation to obtain specific aptamers with high affinity for use in analytical and diagnostic applications. The binding properties or binding domains and their effects on enzyme functions form the basis for therapeutic applications.
In this work, the binding properties of DNA aptamers against two different hydrolases were investigated. In view of their potential utility for analytical methods, aptamers against human urokinase (uPA) and New Delhi metallo-β-lactamase-1 (NDM-1) were evaluated for their binding affinity and specificity using different methods. Using the uPA aptamers, a protocol for measuring the binding kinetics of an aptamer-protein-interaction by surface plasmon resonance spectroscopy (SPR) was developed. Based on the increased expression of uPA in different types of cancer, uPA is discussed as a prognostic and diagnostic tumor marker. As uPA aptamers showed different binding sites on the protein, microtiter plate-based aptamer sandwich assay systems for the detection of uPA were developed. Because of the function of urokinase in cancer cell proliferation and metastasis, uPA is also discussed as a therapeutic target. In this regard, the different binding sites of aptamers showed different effects on uPA function. In vitro experiments demonstrated both inhibition of uPA binding to its receptor as well as the inhibition of uPA catalytic activity for different aptamers. Thus, in addition to their specificity and affinity for their targets, the utility of the aptamers for potential diagnostic and therapeutic applications was demonstrated. First, as an alternative inhibitor of human urokinase for therapeutic purposes, and second, as valuable recognition molecules for the detection of urokinase, as a prognostic and diagnostic marker for cancer, and for NDM-1 to detect resistance to carbapenem antibiotics.
Late-type stars are by far the most frequent stars in the universe and of fundamental interest to various fields of astronomy – most notably to Galactic archaeology and exoplanet research. However, such stars barely change during their main sequence lifetime; their temperature, luminosity, or chemical composition evolve only very slowly over the course of billions of years. As such, it is difficult to obtain the age of such a star, especially when it is isolated and no other indications (like cluster association) can be used. Gyrochronology offers a way to overcome this problem.
Stars, just like all other objects in the universe, rotate and the rate at which stars rotate impacts many aspects of their appearance and evolution. Gyrochronology leverages the observed rotation rate of a late-type main sequence star and its systematic evolution to estimate their ages. Unlike the above-mentioned parameters, the rotation rate of a main sequence star changes drastically throughout its main sequence lifetime; stars spin down. The youngest stars rotate every few hours, whereas much older stars rotate only about once a month, or – in the case of some late M-stars – once in a hundred days. Given that this spindown is systematic (with an additional mass dependence), it gave rise to the idea of using the observed rotation rate of a star (and its mass or a suitable proxy thereof) to estimate a star’s age. This has been explored widely in young stellar open clusters but remains essentially unconstrained for stars older than the sun, and K and M stars older than 1 Gyr.
This thesis focuses on the continued exploration of the spindown behavior to assess, whether gyrochronology remains applicable for stars of old ages, whether it is universal for late-type main sequence stars (including field stars), and to provide calibration mileposts for spindown models. To accomplish this, I have analyzed data from Kepler space telescope for the open clusters Ruprecht 147 (2.7 Gyr old) and M 67 (4 Gyr). Time series photometry data (light curves)
were obtained for both clusters during Kepler’s K2 mission. However, due to technical limitations and telescope malfunctions, extracting usable data from the K2 mission to identify (especially long) rotation periods requires extensive data preparation.
For Ruprecht 147, I have compiled a list of about 300 cluster members from the literature and adopted preprocessed light curves from the Kepler archive where available. They have been cleaned of the gravest of data artifacts but still contained systematics. After correcting them for said artifacts, I was able to identify rotation periods in 31 of them.
For M 67 more effort was taken. My work on Ruprecht 147 has shown the limitations imposed by the preselection of Kepler targets. Therefore, I adopted the time series full frame image directly and performed photometry on a much higher spatial resolution to be able to obtain data for as many stars as possible. This also means that I had to deal with the ubiquitous artifacts in Kepler data. For that, I devised a method that correlates the artificial flux variations with the ongoing drift of the telescope pointing in order to remove it. This process was a large success and I was able to create light curves whose quality match and even exceede those that were created by the Kepler mission – all while operating on higher spatial resolution and processing fainter stars. Ultimately, I was able to identify signs of periodic variability in the (created) light curves for 31 and 47 stars in Ruprecht 147 and M 67, respectively. My data connect well to bluer stars of cluster of the same age and extend for the first time to stars redder than early-K and older than 1 Gyr. The cluster data show a clear flattening in the distribution of Ruprecht 147 and even a downturn for M 67, resulting in a somewhat sinusoidal shape. With that, I have shown that the systematic spindown of stars continues at least until 4 Gyr and stars continue to live on a single surface in age-rotation periods-mass space which allows gyrochronology to be used at least up to that age. However, the shape of the spindown – as exemplified by the newly discovered sinusoidal shape of the cluster sequence – deviates strongly from the expectations.
I then compiled an extensive sample of rotation data in open clusters – very much including my own work – and used the resulting cluster skeleton (with each cluster forming a rip in color-rotation period-mass space) to investigate if field stars follow the same spindown as cluster stars. For the field stars, I used wide binaries, which – with their shared origin and coevality – are in a sense the smallest possible open clusters. I devised an empirical method to evaluate the consistency between the rotation rates of the wide binary components and found that the vast majority of them are in fact consistent with what is observed in open clusters. This leads me to conclude that gyrochronology – calibrated on open clusters – can be applied to determine the ages of field stars.
Amoeboid cell motility takes place in a variety of biomedical processes such as cancer metastasis, embryonic morphogenesis, and wound healing. In contrast to other forms of cell motility, it is mainly driven by substantial cell shape changes. Based on the interplay of explorative membrane protrusions at the front and a slower-acting membrane retraction at the rear, the cell moves in a crawling kind of way. Underlying these protrusions and retractions are multiple physiological processes resulting in changes of the cytoskeleton, a meshwork of different multi-functional proteins. The complexity and versatility of amoeboid cell motility raise the need for novel computational models based on a profound theoretical framework to analyze and simulate the dynamics of the cell shape.
The objective of this thesis is the development of (i) a mathematical framework to describe contour dynamics in time and space, (ii) a computational model to infer expansion and retraction characteristics of individual cell tracks and to produce realistic contour dynamics, (iii) and a complementing Open Science approach to make the above methods fully accessible and easy to use.
In this work, we mainly used single-cell recordings of the model organism Dictyostelium discoideum. Based on stacks of segmented microscopy images, we apply a Bayesian approach to obtain smooth representations of the cell membrane, so-called cell contours. We introduce a one-parameter family of regularized contour flows to track reference points on the contour (virtual markers) in time and space. This way, we define a coordinate system to visualize local geometric and dynamic quantities of individual contour dynamics in so-called kymograph plots. In particular, we introduce the local marker dispersion as a measure to identify membrane protrusions and retractions in a fully automated way.
This mathematical framework is the basis of a novel contour dynamics model, which consists of three biophysiologically motivated components: one stochastic term, accounting for membrane protrusions, and two deterministic terms to control the shape and area of the contour, which account for membrane retractions. Our model provides a fully automated approach to infer protrusion and retraction characteristics from experimental cell tracks while being also capable of simulating realistic and qualitatively different contour dynamics. Furthermore, the model is used to classify two different locomotion types: the amoeboid and a so-called fan-shaped type.
With the complementing Open Science approach, we ensure a high standard regarding the usability of our methods and the reproducibility of our research. In this context, we introduce our software publication named AmoePy, an open-source Python package to segment, analyze, and simulate amoeboid cell motility. Furthermore, we describe measures to improve its usability and extensibility, e.g., by detailed run instructions and an automatically generated source code documentation, and to ensure its functionality and stability, e.g., by automatic software tests, data validation, and a hierarchical package structure.
The mathematical approaches of this work provide substantial improvements regarding the modeling and analysis of amoeboid cell motility. We deem the above methods, due to their generalized nature, to be of greater value for other scientific applications, e.g., varying organisms and experimental setups or the transition from unicellular to multicellular movement. Furthermore, we enable other researchers from different fields, i.e., mathematics, biophysics, and medicine, to apply our mathematical methods. By following Open Science standards, this work is of greater value for the cell migration community and a potential role model for other Open Science contributions.
The field of exercise psychology has established robust evidence on the health benefits of physical activity. However, interventions to promote sustained exercise behavior have often proven ineffective. This dissertation addresses challenges in the field, particularly the neglect of situated and affective processes in understanding and changing exercise behavior. Dual process models, considering both rational and affective processes, have gained recognition. The Affective Reflective Theory of Physical Inactivity and Exercise (ART) is a notable model in this context, positing that situated processes in-the-moment of choice influence exercise decisions and subsequent exercise behavior.
The dissertation identifies current challenges within exercise psychology and proposes methodological and theoretical advancements. It emphasizes the importance of momentary affective states and situated processes, offering alternatives to self-reported measures and advocating for a more comprehensive modeling of individual variability. The focus is on the affective processes during exercise, theorized to reappear in momentary decision-making, shaping overall exercise behavior.
The first publication introduces a new method by using automated facial action analysis to measure variable affective responses during exercise. It explores how these behavioral indicators covary with self-reported measures of affective valence and perceived exertion. The second publication delves into situated processes at the moment of choice between exercise and non-exercise options, revealing that intraindividual factors play a crucial role in explaining exercise-related choices. The third publication presents an open-source research tool, the Decisional Preferences in Exercising Test (DPEX), designed to capture repeated situated decisions and predict exercise behavior based on past experiences.
The findings challenge previous assumptions and provide insights into the complex interplay of affective responses, situated processes, and exercise choices. The dissertation underscores the need for individualized interventions that manipulate affective responses during exercise and calls for systematic testing to establish causal links to automatic affective processes and subsequent exercise behavior. This dissertation highlights the necessity for methodological and conceptual refinements in understanding and promoting exercise behavior, ultimately contributing to the broader goal of combating increasing inactivity trends.
This thesis is concerned with the phenomenon of quantifier scope ambiguities. This phenomenon has been researched extensively, both from a theoretical and from an empirical point of view. Nevertheless, there are still a number of under-researched topics in the field of quantifier scope, which will be the main focus of this thesis. I will take a closer look at three languages, English, German, and the Asante Twi dialect of Akan (Kwa, Niger-Kongo). The goal is a better understanding of the phenomenon of quantifier scope both within each language, as well as from a cross-linguistic perspective. First, this thesis will provide a series of experiments that allow a direct cross-linguistic comparison between English and German – two languages about which specific claims have been made in the literature. I will also provide exploratory research in the case of Asante Twi, where so far, no work has been dedicated specifically to the study of quantifier scope. The work on Asante Twi will go beyond quantifier scope and also target the quantifier and determiner system in general. The question is not only if particular scope readings are possible or not, but also which factors contribute to an increase or decrease of scope availability, and if there are factors that block certain scope readings altogether. While some of the results confirm and thereby strengthen previous claims, other results contradict general assumptions in the literature. This is particularly the case for inverse readings in German and inverse readings across clause-boundaries.
Volcanic hazard assessment relies on physics-based models of hazards, such as lava flows and pyroclastic density currents, whose outcomes are very sensitive to the location where future eruptions will occur. On the contrary, forecast of vent opening locations in volcanic areas typically relies on purely data-driven approaches, where the spatial density of past eruptive vents informs the probability maps of future vent opening. Such techniques may be suboptimal in volcanic systems with missing or scarce data, and where the controls on magma pathways may change over time. An alternative approach was recently proposed, relying on a model of stress-driven pathways of magmatic dikes. In that approach, the crustal stress was optimized so that dike trajectories linked consistently the location of the magma chamber to that of past vents. The retrieved information on the stress state was then used to forecast future dike trajectories. The validation of such an approach requires extensive application to nature. Before doing so, however, several important limitations need to be removed, most importantly the two-dimensional (2D) character of the models and theoretical concepts. In this thesis, I develop methods and tools so that a physics-based strategy of stress inversion and eruptive vent forecast in volcanoes can be applied to three dimensional (3D) problems. In the first part, I test the stress inversion and vent forecast strategy on analog models, still within a 2D framework, but improving on the efficiency of the stress optimization. In the second part, I discuss how to correctly account for gravitational loading/unloading due to complex 3D topography with a Boundary-Element numerical model. Then, I develop a new, simplified but fast model of dike pathways in 3D, designed for running large numbers of simulations at minimal computational cost, and able to backtrack dike trajectories from vents on the surface. Finally, I combine the stress and dike models to simulate dike pathways in synthetic calderas. In the third part, I describe a framework of stress inversion and vent forecast strategy in 3D for calderas. The stress inversion relies on, first, describing the magma storage below a caldera in terms of a probability density function. Next, dike trajectories are backtracked from the known locations of past vents down through the crust, and the optimization algorithm seeks for the stress models which lead trajectories through the regions of highest probability. I apply the new strategy to the synthetic scenarios presented in the second part, and I exploit the results from the stress inversions to produce probability maps of future vent locations for some of those scenarios. In the fourth part, I present the inversion of different deformation source models applied to the ongoing ground deformation observed across the Rhenish Massif in Central Europe. The region includes the Eifel Volcanic Fields in Germany, a potential application case for the vent forecast strategy. The results show how the observed deformation may be due to melt accumulation in sub-horizontal structures in the lower crust or upper mantle. The thesis concludes with a discussion of the stress inversion and vent forecast strategy, its limitations and applicability to real volcanoes. Potential developments of the modeling tools and concepts presented here are also discussed, as well as possible applications to other geophysical problems.
Die finanzgeschichtlichen Untersuchungen sind überwiegend auf Geld konzentriert, Naturalien wurden vernachlässigt oder ausgeblendet. Die vorliegende Arbeit bezieht die Naturalien konsequent mit ein. Nur so ist eine Analyse der Domänenwirtschaft in ihrer Bedeutung für die Staatsfinanzen möglich. Der Erkenntnisfortschritt liegt in der konsequenten Berücksichtigung der Naturalien durch Umrechnung in Geldwerte. Nicht zu leisten ist der Anteil der domänenwirtschaftlichen Erträge am Gesamthaushalt des hessischen Territorialstaates, auch ist die Vermarktung der Überschüsse der Ämter quellenbedingt nicht zu ermitteln. Die Ämterfinanzen zeigen einen Rahmen für domänenwirtschaftliche Staatsfinanzierung auf, dass bei Verzicht auf militärische Aktionen der frühmoderne Territorialstaat domänenwirtschaftlich zu finanzieren war.
Die vorliegende Untersuchung kann aufzeigen, dass der domänenwirtschaftliche Rahmen für die Finanzierung eines Territorialstaates ausreichte, wenn er auf militärische Aktivitäten und Abenteuer verzichtete. In dieser Studie werden erstmalig umfassende statistische Erhebungen der unteren staatlichen Ebene, das Landbuch und das Ämterbuch ausgewertet, die bisher nur von Kersten Krüger ediert waren. Die vorliegende Arbeit ist in die Staatsfinanzierung auf der Stufe der Domänenwirtschaft einzuordnen. Landgraf Wilhelm IV. von Hessen-Kassel war einer der letzten, der es geschafft hatte, seinen Staat domänenwirtschaftlich mit den Einnahmen aus den Naturalien zu finanzieren. Als Domänenstaat wird ein Staat bezeichnet, der auf den ordentlichen Einkünften aus Liegenschaften und Landbesitz beruht. Es wird in dieser Arbeit der domänenwirtschaftliche Rahmen für die Staatsfinanzen berechnet. Das bedeutet, dass die Zentralfinanzen nicht berücksichtigt sind.
Es konnte gezeigt werden, dass, obwohl Landgraf Wilhelm IV. über ein kleineres Territorium als sein Vater, Landgraf Philipp der Großmütige, verfügte, die Gesamtüberschüsse höher waren. Das war seiner klugen Politik zu verdanken und seinen Bemühungen, ständig die Ämterfinanzen zu verbessern. Wilhelm IV. konsolidierte seinen Staat und konnte über domänenwirtschaftliche Einnahmen aus den Ämtern seinen Staat finanzieren. Das gelang ihm, da er erstens seinen Staat ordentlich verwaltete und zweitens keine Kriege führte. Landgraf Wilhelm IV. verabscheute den Krieg. Er sagte über den Krieg: „es ist kain abscheulicher ding auf erden als ein krieg“.
Reactive eutectic media based on ammonium formate for the valorization of bio-sourced materials
(2023)
In the last several decades eutectic mixtures of different compositions were successfully used as solvents for vast amount of chemical processes, and only relatively recently they were discovered to be widely spread in nature. As such they are discussed as a third liquid media of the living cell, that is composed of common cell metabolites. Such media may also incorporate water as a eutectic component in order to regulate properties such as enzyme activity or viscosity. Taking inspiration form such sophisticated use of eutectic mixtures, this thesis will explore the use of reactive eutectic media (REM) for organic synthesis. Such unconventional media are characterized by the reactivity of their components, which means that mixture may assume the role of the solvent as well as the reactant itself.
The thesis focuses on novel REM based on ammonium formate and investigates their potential for the valorization of bio-sourced materials. The use of REM allows the performance of a number of solvent-free reactions, which entails the benefits of a superior atom and energy economy, higher yields and faster rates compared to reactions in solution. This is evident for the Maillard reaction between ammonium formate and various monosaccharides for the synthesis of substituted pyrazines as well as for a Leuckart type reaction between ammonium formate and levulinic acid for the synthesis of 5-methyl-2-pyrrolidone. Furthermore, reaction of ammonium formate with citric acid for the synthesis of yet undiscovered fluorophores, shows that synthesis in REM can open up unexpected reaction pathways.
Another focus of the thesis is the study of water as a third component in the REM. As a result, the concept of two different dilution regimes (tertiary REM and in REM in solvent) appears useful for understanding the influence of water. It is shown that small amounts of water can be of great benefit for the reaction, by reducing viscosity and at the same time increasing reaction yields.
REM based on ammonium formate and organic acids are employed for lignocellulosic biomass treatment. The thesis thereby introduces an alternative approach towards lignocellulosic biomass fractionation that promises a considerable process intensification by the simultaneous generation of cellulose and lignin as well as the production of value-added chemicals from REM components. The thesis investigates the generated cellulose and the pathway to nanocellulose generation and also includes the structural analysis of extracted lignin.
Finally, the thesis investigates the potential of microwave heating to run chemical reactions in REM and describes the synergy between these two approaches. Microwave heating for chemical reactions and the use of eutectic mixtures as alternative reaction media are two research fields that are often described in the scope of green chemistry. The thesis will therefore also contain a closer inspection of this terminology and its greater goal of sustainability.
The Lyman-𝛼 (Ly𝛼) line commonly assists in the detection of high-redshift galaxies, the so-called Lyman-alpha emitters (LAEs). LAEs are useful tools to study the baryonic matter distribution of the high-redshift universe. Exploring their spatial distribution not only reveals the large-scale structure of the universe at early epochs, but it also provides an insight into the early formation and evolution of the galaxies we observe today. Because dark matter halos (DMHs) serve as sites of galaxy formation, the LAE distribution also traces that of the underlying dark matter. However, the details of this relation and their co-evolution over time remain unclear. Moreover, theoretical studies predict that the spatial distribution of LAEs also impacts their own circumgalactic medium (CGM) by influencing their extended Ly𝛼 gaseous halos (LAHs), whose origin is still under investigation. In this thesis, I make several contributions to improve the knowledge on these fields using samples of LAEs observed with the Multi Unit Spectroscopic Explorer (MUSE) at redshifts of 3 < 𝑧 < 6.
Mit dem Alter kann eine Zunahme leichtgradiger Entzündungsprozesse beobachtet werden, von denen angenommen wird, dass sie den typischen, altersbedingten Verlust an Muskelmasse, -kraft und -funktion „befeuern“. Diese als Inflammaging bezeichneten Prozesse können auf ein komplexes Zusammenspiel aus einem dysfunktionalen (viszeralen) Fettgewebe, einer Dysbiose und damit einhergehender mikrobiellen Translokation und geringeren Abwehrfähigkeit sowie einer insgesamt zunehmenden Immunseneszenz zurückgeführt werden. In Summa begünstigt ein pro-inflammatorisches Milieu metabolische Störungen und chronische, altersassoziierte Erkrankungen, die das Entzündungsgeschehen aufrechterhalten oder vorantreiben. Neben einem essenziellen Bewegungsmangel trägt auch eine westlich geprägte, industrialisierte Ernährungsweise zum Entzündungsgeschehen und zur Entwicklung chronischer Erkrankungen bei. Daher liegt die Vermutung nahe, dem Entzündungsgeschehen mit ausreichend Bewegung und einer anti-inflammatorischen Ernährung entgegenzuwirken. In dieser Hinsicht werden insbesondere Omega-3-Fettsäuren (Omega-3) mit anti-inflammatorischen Eigenschaften verbunden. Obwohl ein Zusammenhang zwischen dem ernährungsbedingten Inflammationspotenzial bzw. der Zufuhr von Omega-3 und dem Inflammationsprofil bereits untersucht wurde, fehlen bislang Untersuchungen insbesondere bei älteren Erwachsenen, die den Link zwischen dem Inflammationspotenzial der Ernährung und Sarkopenie-relevanten Muskelparametern herstellen.
Aufgrund des Proteinmehrbedarfs zum Erhalt der funktionellen Muskulatur im Alter wurde bereits eine Vielzahl an Sport- und Ernährungsinterventionen durchgeführt, die eine Verbesserung des Muskelstatus mit Hilfe von strukturiertem Krafttraining und einer proteinreichen Ernährung zeigen. Es gibt zudem Hinweise, dass Omega-3 auch die Proteinsynthese verstärken könnten. Unklar ist jedoch, inwiefern eine anti-inflammatorische Ernährung mit Fokus auf Omega-3 sowohl die Entzündungsprozesse als auch den Muskelproteinmetabolismus und die neuromuskuläre Funktionalität im Alter günstig unterstützen kann. Dies vor allem im Hinblick auf die Muskelleistung, die eng mit der Sturzneigung und der Autonomie im Alltag verknüpft ist, aber in Interventionsstudien mit älteren Erwachsenen bisher wenig Berücksichtigung erhielt. Darüber hinaus werden häufig progressive Trainingselemente genutzt, die nach Studienabschluss oftmals wenig Anschluss im Lebensalltag der Betroffenen finden und somit wenig nachhaltig sind. Ziel dieser Arbeit war demnach die Evaluierung einer proteinreichen und zusätzlich mit Omega-3 supplementierten Ernährung in Kombination mit einem wöchentlichen Vibrationstraining und altersgemäßen Bewegungsprogramm auf Inflammation und neuromuskuläre Funktion bei älteren, selbständig lebenden Erwachsenen.
Hierzu wurden zunächst mögliche Zusammenhänge zwischen dem ernährungsbedingten Inflammationspotenzial, ermittelt anhand des Dietary Inflammatory Index, und dem Muskelstatus sowie dem Inflammationsprofil im Alter eruiert. Dazu dienten die Ausgangswerte von älteren, selbständig lebenden Erwachsenen einer postprandialen Interventionsstudie (POST-Studie), die im Querschnitt analysiert wurden. Die Ergebnisse bestätigten, dass eine pro-inflammatorische Ernährung sich einerseits in einem stärkeren Entzündungsgeschehen widerspiegelt und andererseits mit Sarkopenie-relevanten Parametern, wie einer geringeren Muskelmasse und Gehgeschwindigkeit, ungünstig assoziiert ist. Darüber hinaus zeigten sich diese Zusammenhänge auch in Bezug auf die Handgreifkraft bei den inaktiven, älteren Erwachsenen der Studie.
Anschließend wurde in einer explorativ ausgerichteten Pilot-Interventionsstudie (AIDA-Studie) in einem dreiarmigen Design untersucht, inwieweit sich eine Supplementierung mit Omega-3 unter Voraussetzung einer optimierten Proteinzufuhr und altersgemäßen Sportintervention mit Vibrationstraining auf die neuromuskuläre Funktion und Inflammation bei selbständig lebenden, älteren Erwachsenen auswirkt. Nach acht Wochen Intervention zeigte sich, dass eine mit Omega-3 supplementierte, proteinreiche Ernährung die Muskelleistung insbesondere bei den älteren Männern steigerte. Während sich die Kontrollgruppe nach acht Wochen Sportintervention nicht verbesserte, bestätigte sich zusätzlich eine Verbesserung der Beinkraft und der Testzeit beim Stuhl-Aufsteh-Test der älteren Erwachsenen mit einer proteinreichen Ernährung in Kombination mit der Sportintervention.
Darüber hinaus wurde deutlich, dass die zusätzliche Omega-3-Supplementierung insbesondere bei den Männern eine Reduktion der pro-inflammatorischen Zytokine im Serum zur Folge hatte. Allerdings spiegelten sich diese Beobachtungen nicht auf Genexpressionsebene in mononukleären Immunzellen oder in der LPS-induzierten Sekretion der Zytokine und Chemokine in Vollblutzellkulturen wider. Dies erfordert weitere Untersuchungen.
Soft-template strategy enables the fabrication of composite nanomaterials with desired functionalities and structures. In this thesis, soft templates, including poly(ionic liquid) nanovesicles (PIL NVs), self-assembled polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) particles, and glycopeptide (GP) biomolecules have been applied for the synthesis of versatile composite particles of PILs/Cu, molybdenum disulfide/carbon (MoS2/C), and GP-carbon nanotubes-metal (GP-CNTs-metal) composites, respectively. Subsequently, their possible applications as efficient catalysts in two representative reactions, i.e. CO2 electroreduction (CO2ER) and reduction of 4-nitrophenol (4-NP), have been studied, respectively.
In the first work, PIL NVs with a tunable particle size of 50 to 120 nm and a shell thickness of 15 to 60 nm have been prepared via one-step free radical polymerization. By increasing monomer concentration for polymerization, their nanoscopic morphology can evolve from hollow NVs to dense spheres, and finally to directional worms, in which a multi-lamellar packing of PIL chains occurred in all samples. The obtained PIL NVs with varied shell thickness have been in situ functionalized with ultra-small Cu nanoparticles (Cu NPs, 1-3 nm) and subsequently employed as the electrocatalysts for CO2ER. The hollow PILs/Cu composite catalysts exhibit a 2.5-fold enhancement in selectivity towards C1 products compared to the pristine Cu NPs. This enhancement is primarily attributed to the strong electronic interactions between the Cu NPs and the surface functionalities of PIL NVs. This study casts new aspects on using nanostructured PILs as novel electrocatalyst supports in efficient CO2 conversion.
In the second work, a novel approach towards fast degradation of 4-NP has been developed using porous MoS2/C particles as catalysts, which integrate the intrinsically catalytic property of MoS2 with its photothermal conversion capability. Various MoS2/C composite particles have been prepared using assembled PS-b-P2VP block copolymer particles as sacrificed soft templates. Intriguingly, the MoS2/C particles exhibit tailored morphologies including pomegranate-like, hollow, and open porous structures. Subsequently, the photothermal conversion performance of these featured particles has been compared under near infrared (NIR) light irradiation. When employing the open porous MoS2/C particles as the catalyst for the reduction of 4-NP, the reaction rate constant has increased by 1.5-fold under light illumination. This catalytic enhancement mainly results from the open porous architecture and photothermal conversion performance of the MoS2 particles. This proposed strategy offers new opportunities for efficient photothermal-assisted catalysis.
In the third work, a facile and green approach towards the fabrication of GP-CNTs-metal composites has been proposed, which utilizes a versatile GP biomolecule both as a stabilizer for CNTs in water and as a reducing agent for noble metal ions. The abundant hydrogen bonds in GP molecules bestow the formed GP-CNTs with excellent plasticity, enabling the availability of polymorphic CNTs species ranging from dispersion to viscous paste, gel, and even dough by increasing their concentration. The GP molecules can reduce metal precursors at room temperature without additional reducing agents, enabling the in situ immobilization of metal NPs (e.g. Au, Ag, and Pd) on the CNTs surface. The combination of excellent catalytic property of Pd NPs with photothermal conversion capability of CNTs makes the GP-CNTs-Pd composite a promising catalyst for the efficient degradation of 4-NP. The obtained composite displays a 1.6-fold increase in conversion under NIR light illumination in the reduction of 4-NP, mainly owing to the strong light-to-heat conversion effect of CNTs. Overall, the proposed method opens a new avenue for the synthesis of CNTs composite as a sustainable and versatile catalyst platform.
The results presented in the current thesis demonstrate the significance of using soft templates for the synthesis of versatile composites with tailored nanostructure and functionalities. The investigation of these composite nanomaterials in the catalytic reactions reveals their potential in the development of desired catalysts for emerging catalytic processes, e.g. photothermal-assisted catalysis and electrocatalysis.
The Security Operations Center (SOC) represents a specialized unit responsible for managing security within enterprises. To aid in its responsibilities, the SOC relies heavily on a Security Information and Event Management (SIEM) system that functions as a centralized repository for all security-related data, providing a comprehensive view of the organization's security posture. Due to the ability to offer such insights, SIEMS are considered indispensable tools facilitating SOC functions, such as monitoring, threat detection, and incident response.
Despite advancements in big data architectures and analytics, most SIEMs fall short of keeping pace. Architecturally, they function merely as log search engines, lacking the support for distributed large-scale analytics. Analytically, they rely on rule-based correlation, neglecting the adoption of more advanced data science and machine learning techniques.
This thesis first proposes a blueprint for next-generation SIEM systems that emphasize distributed processing and multi-layered storage to enable data mining at a big data scale. Next, with the architectural support, it introduces two data mining approaches for advanced threat detection as part of SOC operations.
First, a novel graph mining technique that formulates threat detection within the SIEM system as a large-scale graph mining and inference problem, built on the principles of guilt-by-association and exempt-by-reputation. The approach entails the construction of a Heterogeneous Information Network (HIN) that models shared characteristics and associations among entities extracted from SIEM-related events/logs. Thereon, a novel graph-based inference algorithm is used to infer a node's maliciousness score based on its associations with other entities in the HIN. Second, an innovative outlier detection technique that imitates a SOC analyst's reasoning process to find anomalies/outliers. The approach emphasizes explainability and simplicity, achieved by combining the output of simple context-aware univariate submodels that calculate an outlier score for each entry.
Both approaches were tested in academic and real-world settings, demonstrating high performance when compared to other algorithms as well as practicality alongside a large enterprise's SIEM system.
This thesis establishes the foundation for next-generation SIEM systems that can enhance today's SOCs and facilitate the transition from human-centric to data-driven security operations.
Inflammatory bowel diseases (IBD), characterised by a chronic inflammation of the gut wall, develop as consequence of an overreacting immune response to commensal bacteria, caused by a combination of genetic and environmental conditions. Large inter-individual differences in the outcome of currently available therapies complicate the decision for the best option for an individual patient. Predicting the prospects of therapeutic success for an individual patient is currently only possible to a limited extent; for this, a better understanding of possible differences between responders and non-responders is needed.
In this thesis, we have developed a mathematical model describing the most important processes of the gut mucosal immune system on the cellular level. The model is based on literature data, which were on the one hand used (qualitatively) to choose which cell types and processes to incorporate and to derive the model structure, and on the other hand (quantitatively) to derive the parameter values. Using ordinary differential equations, it describes the concentration-time course of neutrophils, macrophages, dendritic cells, T cells and bacteria, each subdivided into different cell types and activation states, in the lamina propria and mesenteric lymph nodes. We evaluate the model by means of simulations of the healthy immune response to salmonella infection and mucosal injury.
A virtual population includes IBD patients, which we define through their initially asymptomatic, but after a trigger chronically inflamed gut wall. We demonstrate the model's usefulness in different analyses: (i) The comparison of virtual IBD patients with virtual healthy individuals shows that the disease is elicited by many small or fewer large changes, and allows to make hypotheses about dispositions relevant for development of the disease. (ii) We simulate the effects of different therapeutic targets and make predictions about the therapeutic outcome based on the pre-treatment state. (iii) From the analysis of differences between virtual responders and non-responders, we derive hypotheses about reasons for the inter-individual variability in treatment outcome. (iv) For the example of anti-TNF-alpha therapy, we analyse, which alternative therapies are most promising in case of therapeutic failure, and which therapies are most suited for combination therapies: For drugs also directly targeting the cytokine levels or inhibiting the recruitment of innate immune cells, we predict a low probability of success when used as alternative treatment, but a large gain when used in a combination treatment. For drugs with direct effects on T cells, via modulation of the sphingosine-1-phosphate receptor or inhibition of T cell proliferation, we predict a considerably larger probability of success when used as alternative treatment, but only a small additional gain when used in a combination therapy.
The near-Earth space environment is a highly complex system comprised of several regions and particle populations hazardous to satellite operations. The trapped particles in the radiation belts and ring current can cause significant damage to satellites during space weather events, due to deep dielectric and surface charging. Closer to Earth is another important region, the ionosphere, which delays the propagation of radio signals and can adversely affect navigation and positioning. In response to fluctuations in solar and geomagnetic activity, both the inner-magnetospheric and ionospheric populations can undergo drastic and sudden changes within minutes to hours, which creates a challenge for predicting their behavior. Given the increasing reliance of our society on satellite technology, improving our understanding and modeling of these populations is a matter of paramount importance.
In recent years, numerous spacecraft have been launched to study the dynamics of particle populations in the near-Earth space, transforming it into a data-rich environment. To extract valuable insights from the abundance of available observations, it is crucial to employ advanced modeling techniques, and machine learning methods are among the most powerful approaches available. This dissertation employs long-term satellite observations to analyze the processes that drive particle dynamics, and builds interdisciplinary links between space physics and machine learning by developing new state-of-the-art models of the inner-magnetospheric and ionospheric particle dynamics.
The first aim of this thesis is to investigate the behavior of electrons in Earth's radiation belts and ring current. Using ~18 years of electron flux observations from the Global Positioning System (GPS), we developed the first machine learning model of hundreds-of-keV electron flux at Medium Earth Orbit (MEO) that is driven solely by solar wind and geomagnetic indices and does not require auxiliary flux measurements as inputs. We then proceeded to analyze the directional distributions of electrons, and for the first time, used Fourier sine series to fit electron pitch angle distributions (PADs) in Earth's inner magnetosphere. We performed a superposed epoch analysis of 129 geomagnetic storms during the Van Allen Probes era and demonstrated that electron PADs have a strong energy-dependent response to geomagnetic activity. Additionally, we showed that the solar wind dynamic pressure could be used as a good predictor of the PAD dynamics. Using the observed dependencies, we created the first PAD model with a continuous dependence on L, magnetic local time (MLT) and activity, and developed two techniques to reconstruct near-equatorial electron flux observations from low-PA data using this model.
The second objective of this thesis is to develop a novel model of the topside ionosphere. To achieve this goal, we collected observations from five of the most widely used ionospheric missions and intercalibrated these data sets. This allowed us to use these data jointly for model development, validation, and comparison with other existing empirical models. We demonstrated, for the first time, that ion density observations by Swarm Langmuir Probes exhibit overestimation (up to ~40-50%) at low and mid-latitudes on the night side, and suggested that the influence of light ions could be a potential cause of this overestimation. To develop the topside model, we used 19 years of radio occultation (RO) electron density profiles, which were fitted with a Chapman function with a linear dependence of scale height on altitude. This approximation yields 4 parameters, namely the peak density and height of the F2-layer and the slope and intercept of the linear scale height trend, which were modeled using feedforward neural networks (NNs). The model was extensively validated against both RO and in-situ observations and was found to outperform the International Reference Ionosphere (IRI) model by up to an order of magnitude. Our analysis showed that the most substantial deviations of the IRI model from the data occur at altitudes of 100-200 km above the F2-layer peak. The developed NN-based ionospheric model reproduces the effects of various physical mechanisms observed in the topside ionosphere and provides highly accurate electron density predictions.
This dissertation provides an extensive study of geospace dynamics, and the main results of this work contribute to the improvement of models of plasma populations in the near-Earth space environment.
This thesis discusses heat and charge transport phenomena in single-crystalline Silicon penetrated by nanometer-sized pores, known as mesoporous Silicon (pSi). Despite the extensive attention given to it as a thermoelectric material of interest, studies on microscopic thermal and electronic transport beyond its macroscopic characterizations are rarely reported. In contrast, this work reports the interplay of both.
PSi samples synthesized by electrochemical anodization display a temperature dependence of specific heat 𝐶𝑝 that deviates from the characteristic 𝑇^3 behaviour (at 𝑇<50𝐾). A thorough analysis reveals that both 3D and 2D Einstein and Debye modes contribute to this specific heat. Additional 2D Einstein modes (~3 𝑚𝑒𝑉) agree reasonably well with the boson peak of SiO2 in pSi pore walls. 2D Debye modes are proposed to account for surface acoustic modes causing a significant deviation from the well-known 𝑇^3 dependence of 𝐶𝑝 at 𝑇<50𝐾.
A novel theoretical model gives insights into the thermal conductivity of pSi in terms of porosity and phonon scattering on the nanoscale. The thermal conductivity analysis utilizes the peculiarities of the pSi phonon dispersion probed by the inelastic neutron scattering experiments. A phonon mean-free path of around 10 𝑛𝑚 extracted from the presented model is proposed to cause the reduced thermal conductivity of pSi by two orders of magnitude compared to p-doped bulk Silicon. Detailed analysis indicates that compound averaging may cause a further 10-50% reduction. The percolation threshold of 65% for thermal conductivity of pSi samples is subsequently determined by employing theoretical effective medium models.
Temperature-dependent electrical conductivity measurements reveal a thermally activated transport process. A detailed analysis of the activation energy 𝐸𝐴𝜎 in the thermally activated transport exhibits a Meyer Neldel compensation rule between different samples that originates in multi-phonon absorption upon carrier transport. Activation energies 𝐸𝐴𝑆 obtained from temperature-dependent thermopower measurements provide further evidence for multi-phonon assisted hopping between localized states as a dominant charge transport mechanism in pSi, as they systematically differ from the determined 𝐸𝐴𝜎 values.
Biomolecules such as proteins and lipids have vital roles in numerous cellular functions, including biomolecule transport, protein functions, cellular homeostasis and biomembrane integrity. Traditional biochemistry methods do not provide precise information about cellular biomolecule distribution and behavior under native environmental conditions since they are not transferable to live cell samples. Consequently, this can lead to inaccuracies in quantifying biomolecule interactions due to potential complexities arising from the heterogeneity of native biomembranes. To overcome these limitations, minimal invasive microscopic techniques, such as fluorescence fluctuation spectroscopy (FFS) in combination with fluorescence proteins (FPs) and fluorescence lipid analogs, have been developed. FFS techniques and membrane property sensors enable the quantification of various parameters, including concentration, dynamics, oligomerization, and interaction of biomolecules in live cell samples.
In this work, several FFS approaches and membrane property sensors were implemented and employed to examine biological processes of diverse context. Multi-color scanning fluorescence fluctuation spectroscopy (sFCS) was used the examine protein oligomerization, protein-protein interactions (PPIs) and protein dynamics at the cellular plasma membrane (PM). Additionally, two-color number and brightness (N&B) analysis was extended with the cross-correlation analysis in order to quantify hetero-interactions of proteins in the PM with very slow motion, which would not accessible with sFCS due strong initial photobleaching. Furthermore, two semi-automatic analysis pipelines were designed: spectral Förster resonance energy transfer (FRET) analysis to study changes in membrane charge at the inner leaflet of the PM, and spectral generalized polarization (GP) imaging and spectral phasor analysis to monitor changes in membrane fluidity and order.
An important parameter for studying PPIs is molecular brightness, which directly determines oligomerization and can be extracted from FFS data. However, FPs often display complex photophysical transitions, including dark states. Therefore, it is crucial to characterize FPs for their dark-states to ensure reliable oligomerization measurements. In this study, N&B and sFCS analysis were applied to determine photophysical properties of novel green FPs under different conditions (i.e., excitation power and pH) in living cells. The results showed that the new FPs, mGreenLantern (mGL) and Gamillus, exhibited the highest molecular brightness at the cost of lower photostability. The well-established monomeric enhanced green fluorescent protein (mEGFP) remained the best option to investigate PPIs at lower pH, while mGL was best suited for neutral pH, and Gamillus for high pH. These findings provide guidance for selecting an appropriate FP to quantify PPIs via FFS under different environmental conditions.
Next, several biophysical fluorescence microscopy approaches (i.e., sFCS, GP imaging, membrane charge FRET) were employed to monitor changes in lipid-lipid-packing in biomembranes in different biological context. Lipid metabolism in cancer cells is known to support rapid proliferation and metastasis. Therefore, targeting lipid synthesis or membrane integrity holds immense promise as an anticancer strategy. However, the mechanism of action of the novel agent erufosine (EPC3) on membrane stability is not fully under
stood. The present work revealed that EPC3 reduces lipid packing and composition as well as increased membrane fluidity and dynamic, hence, modifies lipid-lipid-interaction. These effects on membrane integrity were likely triggered by modulations in lipid metabolism and membrane organization. In the case of influenza A virus (IAV) infection, regulation of lipid metabolism is crucial for multiple steps in IAV replication and is related to the pathogenicity of IAV. Here, it is shown for the first time that IAV infection triggers a local enrichment of negatively charged lipids at the inner leaflet of the PM, which decreases membrane fluidity and dynamic, as well as increases lipid packing at the assembly site in living cells. This suggests that IAV alters lipid-lipid interactions and organization at the PM. Overall, this work highlights the potential of biophysical techniques as a screening platform for studying membrane properties in living cells at the single-cell level.
Finally, this study addressed remaining questions about the early stage of IAV assembly. The recruitment of matrix protein 1 (M1) and its interaction with other viral surface proteins, hemagglutinin (HA), neuraminidase (NA), and matrix protein 2 (M2), has been a subject of debate due to conflicting results. In this study, different FFS approaches were performed in transfected cells to investigate interactions between IAV proteins themselves and host factors at the PM. FFS measurements revealed that M2 interacts strongly with M1, leading to the translocation of M1 to the PM. This interaction likely took place along the non-canonical pathway, as evidenced by the detection of an interaction between M2 and the host factor LC3-II, leading to the recruitment of LC3-II to the PM. Moreover, weaker interaction was observed between HA and membrane-bound M1, and no interaction between NA and M1. Interestingly, higher oligomeric states of M1 were only detectable in infected cells. These results indicate that M2 initiates virion assembly by recruiting M1 to the PM, which may serve as a platform for further interactions with viral proteins and host factors.
Knowledge graphs are structured repositories of knowledge that store facts
about the general world or a particular domain in terms of entities and
their relationships. Owing to the heterogeneity of use cases that are served
by them, there arises a need for the automated construction of domain-
specific knowledge graphs from texts. While there have been many research
efforts towards open information extraction for automated knowledge graph
construction, these techniques do not perform well in domain-specific settings.
Furthermore, regardless of whether they are constructed automatically from
specific texts or based on real-world facts that are constantly evolving, all
knowledge graphs inherently suffer from incompleteness as well as errors in
the information they hold.
This thesis investigates the challenges encountered during knowledge graph
construction and proposes techniques for their curation (a.k.a. refinement)
including the correction of semantic ambiguities and the completion of missing
facts. Firstly, we leverage existing approaches for the automatic construction
of a knowledge graph in the art domain with open information extraction
techniques and analyse their limitations. In particular, we focus on the
challenging task of named entity recognition for artwork titles and show
empirical evidence of performance improvement with our proposed solution
for the generation of annotated training data.
Towards the curation of existing knowledge graphs, we identify the issue of
polysemous relations that represent different semantics based on the context.
Having concrete semantics for relations is important for downstream appli-
cations (e.g. question answering) that are supported by knowledge graphs.
Therefore, we define the novel task of finding fine-grained relation semantics
in knowledge graphs and propose FineGReS, a data-driven technique that
discovers potential sub-relations with fine-grained meaning from existing pol-
ysemous relations. We leverage knowledge representation learning methods
that generate low-dimensional vectors (or embeddings) for knowledge graphs
to capture their semantics and structure. The efficacy and utility of the
proposed technique are demonstrated by comparing it with several baselines
on the entity classification use case.
Further, we explore the semantic representations in knowledge graph embed-
ding models. In the past decade, these models have shown state-of-the-art
results for the task of link prediction in the context of knowledge graph comple-
tion. In view of the popularity and widespread application of the embedding
techniques not only for link prediction but also for different semantic tasks,
this thesis presents a critical analysis of the embeddings by quantitatively
measuring their semantic capabilities. We investigate and discuss the reasons
for the shortcomings of embeddings in terms of the characteristics of the
underlying knowledge graph datasets and the training techniques used by
popular models.
Following up on this, we propose ReasonKGE, a novel method for generating
semantically enriched knowledge graph embeddings by taking into account the
semantics of the facts that are encapsulated by an ontology accompanying the
knowledge graph. With a targeted, reasoning-based method for generating
negative samples during the training of the models, ReasonKGE is able to
not only enhance the link prediction performance, but also reduce the number
of semantically inconsistent predictions made by the resultant embeddings,
thus improving the quality of knowledge graphs.
Kaum eine Studie zum Deutschen Kaiserreich kommt ohne einen Verweis auf die »Preußischen Jahrbücher« als einflussreicher Stimme der Zeit aus, deren Herausgeber Hans Delbrück keine Kontroverse scheute. Jonas Kleins systematische Beziehungsgeschichte untersucht, woher das Vertrauen resultierte, das Hans Delbrück als politischer Intellektueller parteiübergreifend genoss. Indem die wichtigsten innen- und außenpolitischen Krisenherde des Kaiserreichs in den Blick genommen werden, kristallisieren sich die politischen Grundlinien heraus, auf die Delbrück die »Preußischen Jahrbücher« verpflichtete: für einen starken Staat, kulturellen Liberalismus, progressive Sozialpolitik und nationale Integration. Sein unermüdlicher, keineswegs solitärer Kampf für einen »aufgeklärten Konservatismus« zeugt von alternativen Entwicklungsoptionen des Hohenzollernstaates.
Life on Earth is diverse and ranges from unicellular organisms to multicellular creatures like humans. Although there are theories about how these organisms might have evolved, we understand little about how ‘life’ started from molecules. Bottom-up synthetic biology aims to create minimal cells by combining different modules, such as compartmentalization, growth, division, and cellular communication.
All living cells have a membrane that separates them from the surrounding aqueous medium and helps to protect them. In addition, all eukaryotic cells have organelles that are enclosed by intracellular membranes. Each cellular membrane is primarily made of a lipid bilayer with membrane proteins. Lipids are amphiphilic molecules that assemble into molecular bilayers consisting of two leaflets. The hydrophobic chains of the lipids in the two leaflets face each other, and their hydrophilic headgroups face the aqueous surroundings. Giant unilamellar vesicles (GUVs) are model membrane systems that form large compartments with a size of many micrometers and enclosed by a single lipid bilayer. The size of GUVs is comparable to the size of cells, making them good membrane models which can be studied using an optical microscope. However, after the initial preparation, GUV membranes lack membrane proteins which have to be reconstituted into these membranes by subsequent preparation steps. Depending on the protein, it can be either attached via anchor lipids to one of the membrane leaflets or inserted into the lipid bilayer via its transmembrane domains.
The first step is to prepare the GUVs and then expose them to an exterior solution with proteins. Various protocols have been developed for the initial preparation of GUVs. For the second step, the GUVs can be exposed to a bulk solution of protein or can be trapped in a microfluidic device and then supplied with the protein solution. To minimize the amount of solution and for more precise measurements, I have designed a microfluidic device that has a main channel, and several dead-end side channels that are perpendicular to the main channel. The GUVs are trapped in the dead-end channels. This design exchanges the solution around the GUVs via diffusion from the main channel, thus shielding the GUVs from the flow within the main channel. This device has a small volume of just 2.5 μL, can be used without a pump and can be combined with a confocal microscope, enabling uninterrupted imaging of the GUVs during the experiments. I used this device for most of the experiments on GUVs that are discussed in this thesis.
In the first project of the thesis, a lipid mixture doped with an anchor lipid was used that can bind to a histidine chain (referred to as His-tag(ged) or 6H) via the metal cation Ni2+. This method is widely used for the biofunctionalization of GUVs by attaching proteins without a transmembrane domain. Fluorescently labeled His-tags which are bound to a membrane can be observed in a confocal microscope. Using the same lipid mixture, I prepared the GUVs with different protocols and investigated the membrane composition of the resulting GUVs by evaluating the amount of fluorescently labeled His-tagged molecules bound to their membranes. I used the microfluidic device described above to expose the outer leaflet of the vesicle to a constant concentration of the His-tagged molecules. Two fluorescent molecules with a His-tag were studied and compared: green fluorescent protein (6H-GFP) and fluorescein isothiocyanate (6H-FITC). Although the quantum yield in solution is similar for both molecules, the brightness of the membrane-bound 6H-GFP is higher than the brightness of the membrane-bound 6H-FITC. The observed difference in the brightness reveals that the fluorescence of the 6H-FITC is quenched by the anchor lipid via the Ni2+ ion. Furthermore, my measurements also showed that the fluorescence intensity of the membranebound His-tagged molecules depends on microenvironmental factors such as pH. For both 6H-GFP and 6H-FITC, the interaction with the membrane is quantified by evaluating the equilibrium dissociation constant. The membrane fluorescence is measured as a function of the fluorophores’ molar concentration. Theoretical analysis of these data leads to the equilibrium dissociation constants of (37.5 ± 7.5) nM for 6H-GFP and (18.5 ± 3.7) nM for 6H-FITC.
The anchor lipid mentioned previously used the metal cation Ni2+ to mediate the bond between the anchor lipid and the His-tag. The Ni2+ ion can be replaced by other transition metal ions. Studies have shown that Co3+ forms the strongest bonds with the His-tags attached to proteins. In these studies, strong oxidizing agents were used to oxidize the Co2+ mediated complex with the His-tagged protein to a Co3+ mediated complex. This procedure puts the proteins at risk of being oxidized as well. In this thesis, the vesicles were first prepared with anchor lipids without any metal cation. The Co3+ was added to these anchor lipids and finally the His-tagged protein was added to the GUVs to form the Co3+ mediated bond. This system was also established using the microfluidic device.
The different preparation procedures of GUVs usually lead to vesicles with a spherical morphology. On the other hand, many cell organelles have a more complex architecture with a non spherical topology. One fascinating example is provided by the endoplasmic reticulum (ER) which is made of a continuous membrane and extends throughout the cell in the form of tubes and sheets. The tubes are connected by three-way junctions and form a tubular network of irregular polygons. The formation and maintenance of these reticular networks requires membrane proteins that hydrolyize guanosine triphosphate (GTP). One of these membrane proteins is atlastin. In this thesis, I reconstituted the atlastin protein in GUV membranes using detergent-assisted reconstitution protocols to insert the proteins directly into lipid bilayers.
This thesis focuses on protein reconstitution by binding His-tagged proteins to anchor lipids and by detergent-assisted insertion of proteins with transmembrane domains. It also provides the design of a microfluidic device that can be used in various experiments, one example is the evaluation of the equilibrium dissociation constant for membrane-protein interactions. The results of this thesis will help other researchers to understand the protocols for preparing GUVs, to reconstitute proteins in GUVs, and to perform experiments using the microfluidic device. This knowledge should be beneficial for the long-term goal of combining the different modules of synthetic biology to make a minimal cell.
Housing in metabolic cages can induce a pronounced stress response. Metabolic cage systems imply housing mice on metal wire mesh for the collection of urine and feces in addition to monitoring food and water intake. Moreover, mice are single-housed, and no nesting, bedding, or enrichment material is provided, which is often argued to have a not negligible impact on animal welfare due to cold stress. We therefore attempted to reduce stress during metabolic cage housing for mice by comparing an innovative metabolic cage (IMC) with a commercially available metabolic cage from Tecniplast GmbH (TMC) and a control cage. Substantial refinement measures were incorporated into the IMC cage design. In the frame of a multifactorial approach for severity assessment, parameters such as body weight, body composition, food intake, cage and body surface temperature (thermal imaging), mRNA expression of uncoupling protein 1 (Ucp1) in brown adipose tissue (BAT), fur score, and fecal corticosterone metabolites (CMs) were included. Female and male C57BL/6J mice were single-housed for 24 h in either conventional Macrolon cages (control), IMC, or TMC for two sessions. Body weight decreased less in the IMC (females—1st restraint: 6.94%; 2nd restraint: 6.89%; males—1st restraint: 8.08%; 2nd restraint: 5.82%) compared to the TMC (females—1st restraint: 13.2%; 2nd restraint: 15.0%; males—1st restraint: 13.1%; 2nd restraint: 14.9%) and the IMC possessed a higher cage temperature (females—1st restraint: 23.7°C; 2nd restraint: 23.5 °C; males—1st restraint: 23.3 °C; 2nd restraint: 23.5 °C) compared with the TMC (females—1st restraint: 22.4 °C; 2nd restraint: 22.5 °C; males—1st restraint: 22.6 °C; 2nd restraint: 22.4 °C). The concentration of fecal corticosterone metabolites in the TMC (females—1st restraint: 1376 ng/g dry weight (DW); 2nd restraint: 2098 ng/g DW; males—1st restraint: 1030 ng/g DW; 2nd restraint: 1163 ng/g DW) was higher compared to control cage housing (females—1st restraint:
640 ng/g DW; 2nd restraint: 941 ng/g DW; males—1st restraint: 504 ng/g DW; 2nd restraint: 537 ng/g DW). Our results show the stress potential induced by metabolic cage restraint that is markedly influenced by the lower housing temperature. The IMC represents a first attempt to target cold stress reduction during metabolic cage application thereby producing more animal welfare friendly data.
Sulfur is essential for the functionality of some important biomolecules in humans. Biomolecules like the Iron-sulfur clusters, tRNAs, Molybdenum cofactor, and some vitamins. The trafficking of sulfur involves proteins collectively called sulfurtransferase. Among these are TUM1, MOCS3, and NFS1.
This research investigated the role of TUM1 for molybdenum cofactor biosynthesis and cytosolic tRNA thiolation in humans. The rhodanese-like protein MOCS3 and the L-cysteine desulfurase (NFS1) have been previously demonstrated to interact with TUM1. These interactions suggested a dual function of TUM1 in sulfur transfer for Moco biosynthesis and cytosolic tRNA thiolation. TUM1 deficiency has been implicated to be responsible for a rare inheritable disorder known as mercaptolactate cysteine disulfiduria (MCDU), which is associated with a mental disorder. This mental disorder is similar to the symptoms of sulfite oxidase deficiency which is characterised by neurological disorders. Therefore, the role of TUM1 as a sulfurtransferase in humans was investigated, in CRISPR/Cas9 generated TUM1 knockout HEK 293T cell lines.
For the first time, TUM1 was implicated in Moco biosynthesis in humans by quantifying the intermediate product cPMP and Moco using HPLC. Comparing the TUM1 knockout cell lines to the wild-type, accumulation and reduction of cPMP and Moco were observed respectively. The effect of TUM1 knockout on the activity of a Moco-dependent enzyme, Sulfite oxidase, was also investigated. Sulfite oxidase is essential for the detoxification of sulfite to sulfate. Sulfite oxidase activity and protein abundance were reduced due to less availability of Moco. This shows that TUM1 is essential for efficient sulfur transfer for Moco biosynthesis. Reduction in cystathionin -lyase in TUM1 knockout cells was quantified, a possible coping mechanism of the cell against sulfite production through cysteine catabolism.
Secondly, the involvement of TUM1 in tRNA thio-modification at the wobble Uridine-34 was reported by quantifying the amount of mcm5s2U and mcm5U via HPLC. The reduction and accumulation of mcm5s2U and mcm5U in TUM1 knockout cells were observed in the nucleoside analysis. Herein, exogenous treatment with NaHS, a hydrogen sulfide donor, rescued the Moco biosynthesis, cytosolic tRNA thiolation, and cell proliferation deficits in TUM1 knockout cells.
Further, TUM1 was shown to impact mitochondria bioenergetics through the measurement of the oxygen consumption rate and extracellular acidification rate (ECAR) via the seahorse cell Mito stress analyzer. Reduction in total ATP production was also measured. This reveals how important TUM1 is for H2S biosynthesis in the mitochondria of HEK 293T.
Finally, the inhibition of NFS1 in HEK 293T and purified NFS1 protein by 2-methylene 3-quinuclidinone was demonstrated via spectrophotometric and radioactivity quantification. Inhibition of NFS1 by MQ further affected the iron-sulfur cluster-dependent enzyme aconitase activity.
Due to anthropogenic greenhouse gas emissions, Earth’s average surface temperature is steadily increasing. As a consequence, many weather extremes are likely to become more frequent and intense. This poses a threat to natural and human systems, with local impacts capable of destroying exposed assets and infrastructure, and disrupting economic and societal activity. Yet, these effects are not locally confined to the directly affected regions, as they can trigger indirect economic repercussions through loss propagation along supply chains. As a result, local extremes yield a potentially global economic response. To build economic resilience and design effective adaptation measures that mitigate adverse socio-economic impacts of ongoing climate change, it is crucial to gain a comprehensive understanding of indirect impacts and the underlying economic mechanisms.
Presenting six articles in this thesis, I contribute towards this understanding. To this end, I expand on local impacts under current and future climate, the resulting global economic response, as well as the methods and tools to analyze this response.
Starting with a traditional assessment of weather extremes under climate change, the first article investigates extreme snowfall in the Northern Hemisphere until the end of the century. Analyzing an ensemble of global climate model projections reveals an increase of the most extreme snowfall, while mean snowfall decreases.
Assessing repercussions beyond local impacts, I employ numerical simulations to compute indirect economic effects from weather extremes with the numerical agent-based shock propagation model Acclimate. This model is used in conjunction with the recently emerged storyline framework, which involves analyzing the impacts of a particular reference extreme event and comparing them to impacts in plausible counterfactual scenarios under various climate or socio-economic conditions. Using this approach, I introduce three primary storylines that shed light on the complex mechanisms underlying economic loss propagation.
In the second and third articles of this thesis, I analyze storylines for the historical Hurricanes Sandy (2012) and Harvey (2017) in the USA. For this, I first estimate local economic output losses and then simulate the resulting global economic response with Acclimate. The storyline for Hurricane Sandy thereby focuses on global consumption price anomalies and the resulting changes in consumption. I find that the local economic disruption leads to a global wave-like economic price ripple, with upstream effects propagating in the supplier direction and downstream effects in the buyer direction. Initially, an upstream demand reduction causes consumption price decreases, followed by a downstream supply shortage and increasing prices, before the anomalies decay in a normalization phase. A dominant upstream or downstream effect leads to net consumption gains or losses of a region, respectively. Moreover, I demonstrate that a longer direct economic shock intensifies the downstream effect for many regions, leading to an overall consumption loss.
The third article of my thesis builds upon the developed loss estimation method by incorporating projections to future global warming levels. I use these projections to explore how the global production response to Hurricane Harvey would change under further increased global warming. The results show that, while the USA is able to nationally offset direct losses in the reference configuration, other countries have to compensate for increasing shares of counterfactual future losses. This compensation is mainly achieved by large exporting countries, but gradually shifts towards smaller regions. These findings not only highlight the economy’s ability to flexibly mitigate disaster losses to a certain extent, but also reveal the vulnerability and economic disadvantage of regions that are exposed to extreme weather events.
The storyline in the fourth article of my thesis investigates the interaction between global economic stress and the propagation of losses from weather extremes. I examine indirect impacts of weather extremes — tropical cyclones, heat stress, and river floods — worldwide under two different economic conditions: an unstressed economy and a globally stressed economy, as seen during the Covid-19 pandemic. I demonstrate that the adverse effects of weather extremes on global consumption are strongly amplified when the economy is under stress. Specifically, consumption losses in the USA and China double and triple, respectively, due to the global economy’s decreased capacity for disaster loss compensation. An aggravated scarcity intensifies the price response, causing consumption losses to increase.
Advancing on the methods and tools used here, the final two articles in my thesis extend the agent-based model Acclimate and formalize the storyline approach. With the model extension described in the fifth article, regional consumers make rational choices on the goods bought such that their utility is maximized under a constrained budget. In an out-of-equilibrium economy, these rational consumers are shown to temporarily increase consumption of certain goods in spite of rising prices.
The sixth article of my thesis proposes a formalization of the storyline framework, drawing on multiple studies including storylines presented in this thesis. The proposed guideline defines eight central elements that can be used to construct a storyline.
Overall, this thesis contributes towards a better understanding of economic repercussions of weather extremes. It achieves this by providing assessments of local direct impacts, highlighting mechanisms and impacts of loss propagation, and advancing on methods and tools used.
Magmatic-hydrothermal systems form a variety of ore deposits at different proximities to upper-crustal hydrous magma chambers, ranging from greisenization in the roof zone of the intrusion, porphyry mineralization at intermediate depths to epithermal vein deposits near the surface. The physical transport processes and chemical precipitation mechanisms vary between deposit types and are often still debated.
The majority of magmatic-hydrothermal ore deposits are located along the Pacific Ring of Fire, whose eastern part is characterized by the Mesozoic to Cenozoic orogenic belts of the western North and South Americas, namely the American Cordillera. Major magmatic-hydrothermal ore deposits along the American Cordillera include (i) porphyry Cu(-Mo-Au) deposits (along the western cordilleras of Mexico, the western U.S., Canada, Chile, Peru, and Argentina); (ii) Climax- (and sub−) type Mo deposits (Colorado Mineral Belt and northern New Mexico); and (iii) porphyry and IS-type epithermal Sn(-W-Ag) deposits of the Central Andean Tin Belt (Bolivia, Peru and northern Argentina).
The individual studies presented in this thesis primarily focus on the formation of different styles of mineralization located at different proximities to the intrusion in magmatic-hydrothermal systems along the American Cordillera. This includes (i) two individual geochemical studies on the Sweet Home Mine in the Colorado Mineral Belt (potential endmember of peripheral Climax-type mineralization); (ii) one numerical modeling study setup in a generic porphyry Cu-environment; and (iii) a numerical modeling study on the Central Andean Tin Belt-type Pirquitas Mine in NW Argentina.
Microthermometric data of fluid inclusions trapped in greisen quartz and fluorite from the Sweet Home Mine (Detroit City Portal) suggest that the early-stage mineralization precipitated from low- to medium-salinity (1.5-11.5 wt.% equiv. NaCl), CO2-bearing fluids at temperatures between 360 and 415°C and at depths of at least 3.5 km. Stable isotope and noble gas isotope data indicate that greisen formation and base metal mineralization at the Sweet Home Mine was related to fluids of different origins. Early magmatic fluids were the principal source for mantle-derived volatiles (CO2, H2S/SO2, noble gases), which subsequently mixed with significant amounts of heated meteoric water. Mixing of magmatic fluids with meteoric water is constrained by δ2Hw-δ18Ow relationships of fluid inclusions. The deep hydrothermal mineralization at the Sweet Home Mine shows features similar to deep hydrothermal vein mineralization at Climax-type Mo deposits or on their periphery. This suggests that fluid migration and the deposition of ore and gangue minerals in the Sweet Home Mine was triggered by a deep-seated magmatic intrusion.
The second study on the Sweet Home Mine presents Re-Os molybdenite ages of 65.86±0.30 Ma from a Mo-mineralized major normal fault, namely the Contact Structure, and multimineral Rb-Sr isochron ages of 26.26±0.38 Ma and 25.3±3.0 Ma from gangue minerals in greisen assemblages. The age data imply that mineralization at the Sweet Home Mine formed in two separate events: Late Cretaceous (Laramide-related) and Oligocene (Rio Grande Rift-related). Thus, the age of Mo mineralization at the Sweet Home Mine clearly predates that of the Oligocene Climax-type deposits elsewhere in the Colorado Mineral Belt. The Re-Os and Rb-Sr ages also constrain the age of the latest deformation along the Contact Structure to between 62.77±0.50 Ma and 26.26±0.38 Ma, which was employed and/or crosscut by Late Cretaceous and Oligocene fluids. Along the Contact Structure Late Cretaceous molybdenite is spatially associated with Oligocene minerals in the same vein system, a feature that precludes molybdenite recrystallization or reprecipitation by Oligocene ore fluids.
Ore precipitation in porphyry copper systems is generally characterized by metal zoning (Cu-Mo to Zn-Pb-Ag), which is suggested to be variably related to solubility decreases during fluid cooling, fluid-rock interactions, partitioning during fluid phase separation and mixing with external fluids. The numerical modeling study setup in a generic porphyry Cu-environment presents new advances of a numerical process model by considering published constraints on the temperature- and salinity-dependent solubility of Cu, Pb and Zn in the ore fluid. This study investigates the roles of vapor-brine separation, halite saturation, initial metal contents, fluid mixing, and remobilization as first-order controls of the physical hydrology on ore formation. The results show that the magmatic vapor and brine phases ascend with different residence times but as miscible fluid mixtures, with salinity increases generating metal-undersaturated bulk fluids. The release rates of magmatic fluids affect the location of the thermohaline fronts, leading to contrasting mechanisms for ore precipitation: higher rates result in halite saturation without significant metal zoning, lower rates produce zoned ore shells due to mixing with meteoric water. Varying metal contents can affect the order of the final metal precipitation sequence. Redissolution of precipitated metals results in zoned ore shell patterns in more peripheral locations and also decouples halite saturation from ore precipitation.
The epithermal Pirquitas Sn-Ag-Pb-Zn mine in NW Argentina is hosted in a domain of metamorphosed sediments without geological evidence for volcanic activity within a distance of about 10 km from the deposit. However, recent geochemical studies of ore-stage fluid inclusions indicate a significant contribution of magmatic volatiles. This study tested different formation models by applying an existing numerical process model for porphyry-epithermal systems with a magmatic intrusion located either at a distance of about 10 km underneath the nearest active volcano or hidden underneath the deposit. The results show that the migration of the ore fluid over a 10-km distance results in metal precipitation by cooling before the deposit site is reached. In contrast, simulations with a hidden magmatic intrusion beneath the Pirquitas deposit are in line with field observations, which include mineralized hydrothermal breccias in the deposit area.
Hybrid nanomaterials offer the combination of individual properties of different types of nanoparticles. Some strategies for the development of new nanostructures in larger scale rely on the self-assembly of nanoparticles as a bottom-up approach. The use of templates provides ordered assemblies in defined patterns. In a typical soft-template, nanoparticles and other surface-active agents are incorporated into non-miscible liquids. The resulting self-organized dispersions will mediate nanoparticle interactions to control the subsequent self-assembly. Especially interactions between nanoparticles of very different dispersibility and functionality can be directed at a liquid-liquid interface.
In this project, water-in-oil microemulsions were formulated from quasi-ternary mixtures with Aerosol-OT as surfactant. Oleyl-capped superparamagnetic iron oxide and/or silver nanoparticles were incorporated in the continuous organic phase, while polyethyleneimine-stabilized gold nanoparticles were confined in the dispersed water droplets. Each type of nanoparticle can modulate the surfactant film and the inter-droplet interactions in diverse ways, and their combination causes synergistic effects. Interfacial assemblies of nanoparticles resulted after phase-separation. On one hand, from a biphasic Winsor type II system at low surfactant concentration, drop-casting of the upper phase afforded thin films of ordered nanoparticles in filament-like networks. Detailed characterization proved that this templated assembly over a surface is based on the controlled clustering of nanoparticles and the elongation of the microemulsion droplets. This process offers versatility to use different nanoparticle compositions by keeping the surface functionalization, in different solvents and over different surfaces. On the other hand, a magnetic heterocoagulate was formed at higher surfactant concentration, whose phase-transfer from oleic acid to water was possible with another auxiliary surfactant in ethanol-water mixture. When the original components were initially mixed under heating, defined oil-in-water, magnetic-responsive nanostructures were obtained, consisting on water-dispersible nanoparticle domains embedded by a matrix-shell of oil-dispersible nanoparticles.
Herein, two different approaches were demonstrated to form diverse hybrid nanostructures from reverse microemulsions as self-organized dispersions of the same components. This shows that microemulsions are versatile soft-templates not only for the synthesis of nanoparticles, but also for their self-assembly, which suggest new approaches towards the production of new sophisticated nanomaterials in larger scale.
Arthur Schopenhauer (1788–1860) was perhaps the last polymath among the great Germanic philosophers. Switching with ease and elegance between epistemic positions and fields as diverse as idealism and empiricism, fideism and rationalism, realism and nominalism, art and religion, jurisprudence and politics, psychology and occultism, Schopenhauer erected an imposing edifice bearing testimony to his universal learning. This study is an investigation into the very conclusion of Schopenhauer’s philosophy and endeavours to answer the following question: did Schopenhauer’s doctrine of salvation issue forth organically from his intellectual output or was it annexed to his philosophy as a result of his critical engagement with religion? The labyrinthine paths through which Schopenhauer arrives at the soteriological culmination of his philosophy are subjected to critical assessment; the picture that emerges is of a philosopher who seemed convinced that he had solved some of the most pressing cosmic riddles to have tormented mankind through the ages.
Volcanoes are one of the Earth’s most dynamic zones and responsible for many changes in our planet. Volcano seismology aims to provide an understanding of the physical processes in volcanic systems and anticipate the style and timing of eruptions by analyzing the seismic records. Volcanic tremor signals are usually observed in the seismic records before or during volcanic eruptions. Their analysis contributes to evaluate the evolving volcanic activity and potentially predict eruptions. Years of continuous seismic monitoring now provide useful information for operational eruption forecasting. The continuously growing amount of seismic recordings, however, poses a challenge for analysis, information extraction, and interpretation, to support timely decision making during volcanic crises. Furthermore, the complexity of eruption processes and precursory activities makes the analysis challenging.
A challenge in studying seismic signals of volcanic origin is the coexistence of transient signal swarms and long-lasting volcanic tremor signals. Separating transient events from volcanic tremors can, therefore, contribute to improving our understanding of the underlying physical processes. Some similar issues (data reduction, source separation, extraction, and classification) are addressed in the context of music information retrieval (MIR). The signal characteristics of acoustic and seismic recordings comprise a number of similarities. This thesis is going beyond classical signal analysis techniques usually employed in seismology by exploiting similarities of seismic and acoustic signals and building the information retrieval strategy on the expertise developed in the field of MIR.
First, inspired by the idea of harmonic–percussive separation (HPS) in musical signal processing, I have developed a method to extract harmonic volcanic tremor signals and to detect transient events from seismic recordings. This provides a clean tremor signal suitable for tremor investigation along with a characteristic function suitable for earthquake detection. Second, using HPS algorithms, I have developed a noise reduction technique for seismic signals. This method is especially useful for denoising ocean bottom seismometers, which are highly contaminated by noise. The advantage of this method compared to other denoising techniques is that it doesn’t introduce distortion to the broadband earthquake waveforms, which makes it reliable for different applications in passive seismological analysis. Third, to address the challenge of extracting information from high-dimensional data and investigating the complex eruptive phases, I have developed an advanced machine learning model that results in a comprehensive signal processing scheme for volcanic tremors. Using this method seismic signatures of major eruptive phases can be automatically detected. This helps to provide a chronology of the volcanic system. Also, this model is capable to detect weak precursory volcanic tremors prior to the eruption, which could be used as an indicator of imminent eruptive activity. The extracted patterns of seismicity and their temporal variations finally provide an explanation for the transition mechanism between eruptive phases.
Predator-forager interactions are a major factor in evolutionary adaptation of many species, as predators need to gain energy by consuming prey species, and foragers needs to avoid the worst fate of mortality while still consuming resources for energetic gains. In this evolutionary arms race, the foragers have constantly evolved anti-predator behaviours (e.g. foraging activity changes). To describe all these complex changes, researchers developed the framework of the landscape of fear, that is, the spatio-temporal variation of perceived predation risk. This concept simplifies all the involved ecological processes into one framework, by integrating animal biology and distribution with habitat characteristics. Researchers can then evaluate the perception of predation risk in prey species, what are the behavioural responses of the prey and, therefore, understand the cascading effects of landscapes of fear at the resource levels (tri-trophic effects). Although tri-trophic effects are well studied at the predator-prey interaction level, little is known on how the forager-resource interactions are part of the overall cascading effects of landscapes of fear, despite the changes of forager feeding behaviour - that occur with perceived predation risk - affecting directly the level of the resources.
This thesis aimed to evaluate the cascading effects of the landscape of fear on biodiversity of resources, and how the feeding behaviour and movement of foragers shaped the final resource species composition (potential coexistence mechanisms). We studied the changes caused by landscapes of fear on wild and captive rodent communities and evaluated: the cascading effects of different landscapes of fear on a tri-trophic system (I), the effects of fear on a forager’s movement patterns and dietary preferences (II) and cascading effects of different types of predation risk (terrestrial versus avian, III).
In Chapter I, we applied a novel measure to evaluate the cascading effects of fear at the level of resources, by quantifying the diversity of resources left after the foragers gave-up on foraging (diversity at the giving-up density). We tested the measure at different spatial levels (local and regional) and observed that with decreased perceived predation risk, the density and biodiversity of resources also decreased. Foragers left a very dissimilar community of resources based on perceived risk and resources functional traits, and therefore acted as an equalising mechanism.
In Chapter II, we wanted to understand further the decision-making processes of rodents in different landscapes of fear, namely, in which resource species rodents decided to forage on (based on three functional traits: size, nutrients and shape) and how they moved depending on perceived predation risk. In safe landscapes, individuals increased their feeding activity and movements and despite the increased costs, they visited more often patches that were further away from their central-place. Despite a preference for the bigger resources regardless of risk, when perceived predation risk was low, individuals changed their preference to fat-rich resources.
In Chapter III, we evaluated the cascading effects of two different types of predation risk in rodents: terrestrial (raccoon) versus avian predation risk. Raccoon presence or absence did not alter the rodents feeding behaviour in different landscapes of fear. Rodent’s showed risk avoidance behaviours towards avian predators (spatial risk avoidance), but not towards raccoons (lack of temporal risk avoidance).
By analysing the effects of fear in tri-trophic systems, we were able to deepen the knowledge of how non-consumptive effects of predators affect the behaviour of foragers, and quantitatively measure the cascading effects at the level of resources with a novel measure. Foragers are at the core of the ecological processes and responses to the landscape of fear, acting as variable coexistence agents for resource species depending on perceived predation risk. This newly found measures and knowledge can be applied to more trophic chains, and inform researchers on biodiversity patterns originating from landscapes of fear.
Continental rifts are key geodynamic regions where the complex interplay of magmatism and faulting activity can be studied to understand the driving forces of extension and the formation of new divergent plate boundaries. Well-preserved rift morphology can provide a wealth of information on the growth, interaction, and linkage of normal-fault systems through time. If rift basins are preserved over longer geologic time periods, sedimentary archives generated during extensional processes may mirror tectonic and climatic influences on erosional and sedimentary processes that have varied over time. Rift basins are furthermore strategic areas for hydrocarbon and geothermal energy exploration, and they play a central role in species dispersal and evolution as well as providing or inhibiting hydrologic connectivity along basins at emerging plate boundaries.
The Cenozoic East African rift system (EARS) is one of the most important continental extension zones, reflecting a range of evolutionary stages from an early rift stage with isolated basins in Malawi to an advanced stage of continental extension in southern Afar. Consequently, the EARS is an ideal natural laboratory that lends itself to the study of different stages in the breakup of a continent. The volcanically and seismically active eastern branch of the EARS is characterized by multiple, laterally offset tectonic and magmatic segments where adjacent extensional basins facilitate crustal extension either across a broad deformation zone or via major transfer faulting. The Broadly Rifted Zone (BRZ) in southern Ethiopia is an integral part of the eastern branch of the EARS; in this region, rift segments of the southern Ethiopian Rift (sMER) and northern Kenyan Rift (nKR) propagate in opposite directions in a region with one of the earliest manifestations of volcanism and extensional tectonism in East Africa. The basin margins of the Chew-Bahir Basin and the Gofa Province, characterized by a semi-arid climate and largely uniform lithology, provide ideal conditions for studying the tectonic and geomorphologic features of this complex kinematic transfer zone, but more importantly, this area is suitable for characterizing and quantifying the overlap between the propagating structures of the sMER and nKR and the resulting deformation patterns of the BRZ transfer zones.
In this study, I have combined data from thermochronology, thermal modeling, morphometry, paleomagnetic analysis, geochronology, and geomorphological field observations with information from published studies to reconstruct the spatiotemporal relationship between volcanism and fault activity in the BRZ and quantify the deformation patterns of the overlapping rift segments. I present the following results: (1) new thermochronological data from the en-échelon basin margins and footwall blocks of the rift flanks and morphometric results verified in the field to link different phases of magmatism and faulting during extension and infer geomorphological landscape features related to the current tectonic interaction between the nKR and the sMER; (2) temporally constrained paleomagnetic data from the BRZ overlap zone between the Ethiopian and Kenyan rifts to quantitatively determine block rotation between the two segments. Combining the collected data, time-temperature histories of thermal modeling results from representative samples show well-defined deformation phases between 25–20 Ma, 15–9Ma, and ~5 Ma to the present. Each deformation phase is characterized by the onset of rapid cooling (>2°C/Ma) of the crust associated with uplift or exhumation of the rift shoulder. After an initial, spatially very diffuse phase of extension, the rift has gradually evolved into a system of connected structures formed in an increasingly focused rift zone during the last 5 Ma. Regarding the morphometric analysis of the rift structures, it can be shown that normalized slope indices of the river courses, spatial arrangement of knickpoints in the river longitudinal profiles of the footwall blocks, local relief values, and the average maximum values of the slope of the river profiles indicate a gradual increase in the extension rate from north (Sawula basin: mature) to south (Chew Bahir: young). The complexity of the structural evolution of the BRZ overlap zone between nKR and sMER is further emphasized by the documentation of crustal blocks around a vertical axis. A comparison of the mean directions obtained for the Eo-Oligocene (Ds=352.6°, Is=-17.0°, N=18, α95=5.5°) and Miocene (Ds=2.9°, Is=0.9°, N=9, α95=12.4°) volcanics relative to the pole for stable South Africa and with respect to the corresponding ages of the analyzed units record a significant counterclockwise rotation of ~11.1°± 6.4° and insignificant CCW rotation of ~3.2° ± 11.5°, respectively.
My thesis chiefly aims to shed light on the favourable properties of LHP semiconductors from the point of view of their electronic structure.
Currently, various hypotheses are circulating to explain the exceptionally favourable transport properties of LHPs. Seeking an explanation for the low non-radiative recombination rates and long carrier lifetimes is particularly interesting to the halide perovskites research community.
The first part of this work investigates the two main hypotheses that are believed to play a significant role: the existence of a giant Rashba effect and large polarons. The experimental method of ARPES is mainly applied to verify their credibility.
The first hypothesis presumes that a giant Rashba effect restricts the recombination losses of the charge carriers by making the band gap slightly indirect. The Rashba effect is based on a strong SOC that could appear in LHPs thanks to incorporating the heavy element Pb in their structure. Earlier experimental work had pointed out this effect at the VBM of a hybrid LHP as a viable explanation for the long lifetimes of the charge carriers.
My systematic ARPES studies on hybrid MAPbBr3 and spin-resolved ARPES studies on the inorganic CsPbBr3 disprove the presence of any Rashba effect in the VBM of the reported order of magnitude. Therefore, neither the spin texture nor an indirect band gap character at the VBM in the bulk or at the surface can explain the high efficiency of LHP. In case of existence, this effect is in terms of the Rashba parameter at least a factor of a hundred smaller than previously assumed.
The second hypothesis proposes large polaron formation in the electronic structure of LHPs and attributes it to their high defect tolerance and low non-radiative recombination rate. Because the perovskite structure consists of negative and positive ions, polarons of this kind can be expected due to the Coulomb interaction between carriers and the polar lattice at intermediate electron-phonon coupling strength. Their existence is proposed to screen the carriers and defects to avoid recombination and trapping, thus leading to long carrier lifetimes. ARPES results by one group supported this assumption, reporting a 50% effective mass enhancement over the theoretical effective mass for CsPbBr3 in the orthorhombic structure.
The current thesis examines this hypothesis experimentally by photon-energy-dependent ARPES spectra and theoretically by GW band calculations of CsPbBr3 perovskites. The investigation is based on the fact that a polaron contribution in charge transport can become evident by an increase of the effective mass as measured by ARPES over the calculated one without polaron effects. However, my experiments on crystalline CsPbBr3 did not imply a larger effective mass for which one could postulate large polarons. In fact, the effective masses determined from ARPES agree with that of theoretical predictions.
The second part of my thesis thoroughly investigates the possibility of spontaneously magnetizing LHPs by introducing Mn2+ ions. Mn doping was reported to cause ferromagnetism in one of the most common LHPs, MAPbI3, mediated by super-exchange. The current work investigates the magnetic properties of a wide concentration range of Mn-doped MAPbI3 and triple-cation films by XAS, XMCD, and SQUID measurements. Based on the XAS line shape and a sum-rule analysis of the XMCD spectra, a pure Mn2+ configuration has been confirmed. Negative Curie temperatures are extracted from fitting the magnetization with a Curie-Weiss law. However, a remanent magnetization, which would be an indication of the absence of ferromagnetism down to 2K. As far as the double exchange is concerned, the element-specific XAS excludes a sufficient amount of Mn3+ as a prerequisite for this mechanism. All the findings show no evidence of significant double exchange or ferromagnetism in Mn-doped LHPs. The magnetic behavior is paramagnetic rather than ferromagnetic.
In the dissertation's last chapter, orthorhombic features of CsPbBr3 are revealed by ARPES, including an extra VBM at the Γ-point. The VBM of CsPbBr3 shows a temperature-dependent splitting, which decreases by 190 meV between 38K and 300K and tracks a shift of a saddle point at the cubic M-point. It is possible to reproduce the energy shift using an atomic model with a larger unit cell for room temperature, allowing local inversion symmetry breaking. This indicates the importance of electric dipoles for the inorganic LHPs, which may contribute to their high efficiency by breaking inversion symmetry and a Berry-phase effect.
Modern datasets often exhibit diverse, feature-rich, unstructured data, and they are massive in size. This is the case of social networks, human genome, and e-commerce databases. As Artificial Intelligence (AI) systems are increasingly used to detect pattern in data and predict future outcome, there are growing concerns on their ability to process large amounts of data. Motivated by these concerns, we study the problem of designing AI systems that are scalable to very large and heterogeneous data-sets.
Many AI systems require to solve combinatorial optimization problems in their course of action. These optimization problems are typically NP-hard, and they may exhibit additional side constraints. However, the underlying objective functions often exhibit additional properties. These properties can be exploited to design suitable optimization algorithms. One of these properties is the well-studied notion of submodularity, which captures diminishing returns. Submodularity is often found in real-world applications. Furthermore, many relevant applications exhibit generalizations of this property.
In this thesis, we propose new scalable optimization algorithms for combinatorial problems with diminishing returns. Specifically, we focus on three problems, the Maximum Entropy Sampling problem, Video Summarization, and Feature Selection. For each problem, we propose new algorithms that work at scale. These algorithms are based on a variety of techniques, such as forward step-wise selection and adaptive sampling. Our proposed algorithms yield strong approximation guarantees, and the perform well experimentally.
We first study the Maximum Entropy Sampling problem. This problem consists of selecting a subset of random variables from a larger set, that maximize the entropy. By using diminishing return properties, we develop a simple forward step-wise selection optimization algorithm for this problem. Then, we study the problem of selecting a subset of frames, that represent a given video. Again, this problem corresponds to a submodular maximization problem. We provide a new adaptive sampling algorithm for this problem, suitable to handle the complex side constraints imposed by the application. We conclude by studying Feature Selection. In this case, the underlying objective functions generalize the notion of submodularity. We provide a new adaptive sequencing algorithm for this problem, based on the Orthogonal Matching Pursuit paradigm.
Overall, we study practically relevant combinatorial problems, and we propose new algorithms to solve them. We demonstrate that these algorithms are suitable to handle massive datasets. However, our analysis is not problem-specific, and our results can be applied to other domains, if diminishing return properties hold. We hope that the flexibility of our framework inspires further research into scalability in AI.
Depressive disorders are associated with reduced life satisfaction and ability to work. The waiting time for psychotherapy in Germany is currently between three and six months. Accordingly, there is a need for alternative, evidence-based treatment options that are made accessible to patients at a low threshold. A large number of empirical studies prove the effectiveness of exercise in mild and moderate depression. For further conceptualization and quality assurance of exercise as a treatment option, it is necessary to understand the concrete mechanisms of action. In addition to physiological factors, psychological factors also play a role in the effect. As a meta-theory of human experience and behavior, Self-Determination Theory (SDT) provides a useful frame for understanding psychological mechanisms of action with concrete implications for treatment practice. The conceptual extension of SDT to include the frustration of basic psychological needs in addition to need satisfaction is proving useful in the study of mental illness. The first part of this dissertation consists of two publications that validate relevant measurement instruments in this context. The first questionnaire measures the extent of generally experienced satisfaction and frustration of the basic psychological needs for autonomy, competence, and relatedness. The second questionnaire measures the experienced satisfaction of needs by the instructor (here: exercise therapist). The second part of the dissertation includes two publications that examine and classify the satisfaction and frustration of basic psychological needs in depressive symptoms. Differences in the extent of need satisfaction and need frustration between a sample with depression and a sample without depressive symptoms are examined. Further, the relationship between need frustration and depressive symptoms is placed in the context of established pathological processes (emotional dysregulation, rumination). The main findings of this work show that by adding the dimension of need frustration to Basic Psychological Needs Theory, SDT now covers a broader spectrum on the health-disease continuum. In doing so, SDT focuses on the psychological impact of social environments. In addition to the nonfulfillment of basic psychological needs, it is primarily experienced need frustration that is a general vulnerability factor for the occurrence of psychological illness. Moreover, the unbalanced satisfaction of basic psychological needs possibly indicates a conflicting experience between the needs. For the treatment practice it can be deduced that an autonomy-supporting atmosphere, which enables the balanced satisfaction of all three needs, is central for the treatment success.
Solar photocatalysis is the one of leading concepts of research in the current paradigm of sustainable chemical industry. For actual practical implementation of sunlight-driven catalytic processes in organic synthesis, a cheap, efficient, versatile and robust heterogeneous catalyst is necessary. Carbon nitrides are a class of organic semiconductors who are known to fulfill these requirements.
First, current state of solar photocatalysis in economy, industry and lab research is overviewed, outlining EU project funding, prospective synthetic and reforming bulk processes, small scale solar organic chemistry, and existing reactor designs and prototypes, concluding feasibility of the approach.
Then, the photocatalytic aerobic cleavage of oximes to corresponding aldehydes and ketones by anionic poly(heptazine imide) carbon nitride is discussed. The reaction provides a feasible method of deprotection and formation of carbonyl compounds from nitrosation products and serves as a convenient model to study chromoselectivity and photophysics of energy transfer in heterogeneous photocatalysis.
Afterwards, the ability of mesoporous graphitic carbon nitride to conduct proton-coupled electron transfer was utilized for the direct oxygenation of 1,3-oxazolidin-2-ones to corresponding 1,3-oxazlidine-2,4-diones. This reaction provides an easier access to a key scaffold of diverse types of drugs and agrochemicals.
Finally, a series of novel carbon nitrides based on poly(triazine imide) and poly(heptazine imide) structure was synthesized from cyanamide and potassium rhodizonate. These catalysts demonstrated a good performance in a set of photocatalytic benchmark reactions, including aerobic oxidation, dual nickel photoredox catalysis, hydrogen peroxide evolution and chromoselective transformation of organosulfur precursors.
Concluding, the scope of carbon nitride utilization for net-oxidative and net-neutral photocatalytic processes was expanded, and a new tunable platform for catalyst synthesis was discovered.
Essays in public economics
(2023)
This cumulative dissertation uses economic theory and micro-econometric tools and evaluation methods to analyse public policies and their impact on welfare and individual behaviour. In particular, it focuses on policies in two distinct areas that represent fundamental societal challenges in the 21st century: the ageing of society and life in densely-populated urban agglomerations. Together, these areas shape important financial decisions in a person's life, impact welfare, and are driving forces behind many of the challenges in today's societies. The five self-contained research chapters of this thesis analyse the forward looking effects of pension reforms, affordable housing policies as well as a public transport subsidy and its effect on air pollution.
The Andes reflect Cenozoic deformation and uplift along the South American margin in the context of regional shortening associated with the interaction between the subducting Nazca plate and the overriding continental South American plate. Simultaneously, multiple levels of uplifted marine terraces constitute laterally continuous geomorphic features related to the accumulation of permanent forearc deformation in the coastal realm. However, the mechanisms responsible for permanent coastal uplift and the persistency of current/decadal deformation patterns over millennial timescales are still not fully understood. This dissertation presents a continental-scale database of last interglacial terrace elevations and uplift rates along the South American coast that provides the basis for an analysis of a variety of mechanisms that are possibly responsible for the accumulation of permanent coastal uplift. Regional-scale mapping and analysis of multiple, late Pleistocene terrace levels in central Chile furthermore provide valuable insights regarding the persistency of current seismic asperities, the role of upper-plate faulting, and the impact of bathymetric ridges on permanent forearc deformation.
The database of last interglacial terrace elevations reveals an almost continuous signal of background-uplift rates along the South American coast at ~0.22 mm/yr that is modified by various short- to long-wavelength changes. Spatial correlations with crustal faults and subducted bathymetric ridges suggest long-term deformation to be affected by these features, while the latitudinal variability of climate forcing factors has a profound impact on the generation and preservation of marine terraces. Systematic wavelength analyses and comparisons of the terrace-uplift rate signal with different tectonic parameters reveal short-wavelength deformation to result from crustal faulting, while intermediate- to long-wavelength deformation might indicate various extents of long-term seismotectonic segments on the megathrust, which are at least partially controlled by the subduction of bathymetric anomalies. The observed signal of background-uplift rate is likely accumulated by moderate earthquakes near the Moho, suggesting multiple, spatiotemporally distinct phases of uplift that manifest as a continuous uplift signal over millennial timescales.
Various levels of late Pleistocene marine terraces in the 2015 M8.3 Illapel-earthquake area reveal a range of uplift rates between 0.1 and 0.6 mm/yr and indicate decreasing uplift rates since ~400 ka. These glacial-cycle uplift rates do not correlate with current or decadal estimates of coastal deformation suggesting seismic asperities not to be persistent features on the megathrust that control the accumulation of permanent forearc deformation over long timescales of 105 years. Trench-parallel, crustal normal faults modulate the characteristics of permanent forearc-deformation; upper-plate extension likely represents a second-order phenomenon resulting from subduction erosion and subsequent underplating that lead to regional tectonic uplift and local gravitational collapse of the forearc. In addition, variable activity with respect to the subduction of the Juan Fernández Ridge can be detected in the upper plate over the course of multiple interglacial periods, emphasizing the role of bathymetric anomalies in causing local increases in terrace-uplift rate. This thesis therefore provides new insights into the current understanding of subduction-zone processes and the dynamics of coastal forearc deformation, whose different interacting forcing factors impact the topographic and geomorphic evolution of the western South American coast.
Extreme flooding displaces an average of 12 million people every year. Marginalized populations in low-income countries are in particular at high risk, but also industrialized countries are susceptible to displacement and its inherent societal impacts. The risk of being displaced results from a complex interaction of flood hazard, population exposed in the floodplains, and socio-economic vulnerability. Ongoing global warming changes the intensity, frequency, and duration of flood hazards, undermining existing protection measures. Meanwhile, settlements in attractive yet hazardous flood-prone areas have led to a higher degree of population exposure. Finally, the vulnerability to displacement is altered by demographic and social change, shifting economic power, urbanization, and technological development. These risk components have been investigated intensively in the context of loss of life and economic damage, however, only little is known about the risk of displacement under global change.
This thesis aims to improve our understanding of flood-induced displacement risk under global climate change and socio-economic change. This objective is tackled by addressing the following three research questions. First, by focusing on the choice of input data, how well can a global flood modeling chain reproduce flood hazards of historic events that lead to displacement? Second, what are the socio-economic characteristics that shape the vulnerability to displacement? Finally, to what degree has climate change potentially contributed to recent flood-induced displacement events?
To answer the first question, a global flood modeling chain is evaluated by comparing simulated flood extent with satellite-derived inundation information for eight major flood events. A focus is set on the sensitivity to different combinations of the underlying climate reanalysis datasets and global hydrological models which serve as an input for the global hydraulic model. An evaluation scheme of performance scores shows that simulated flood extent is mostly overestimated without the consideration of flood protection and only for a few events dependent on the choice of global hydrological models. Results are more sensitive to the underlying climate forcing, with two datasets differing substantially from a third one. In contrast, the incorporation of flood protection standards results in an underestimation of flood extent, pointing to potential deficiencies in the protection level estimates or the flood frequency distribution within the modeling chain.
Following the analysis of a physical flood hazard model, the socio-economic drivers of vulnerability to displacement are investigated in the next step. For this purpose, a satellite- based, global collection of flood footprints is linked with two disaster inventories to match societal impacts with the corresponding flood hazard. For each event the number of affected population, assets, and critical infrastructure, as well as socio-economic indicators are computed. The resulting datasets are made publicly available and contain 335 displacement events and 695 mortality/damage events. Based on this new data product, event-specific displacement vulnerabilities are determined and multiple (national) dependencies with the socio-economic predictors are derived. The results suggest that economic prosperity only partially shapes vulnerability to displacement; urbanization, infant mortality rate, the share of elderly, population density and critical infrastructure exhibit a stronger functional relationship, suggesting that higher levels of development are generally associated with lower vulnerability.
Besides examining the contextual drivers of vulnerability, the role of climate change in the context of human displacement is also being explored. An impact attribution approach is applied on the example of Cyclone Idai and associated extreme coastal flooding in Mozambique. A combination of coastal flood modeling and satellite imagery is used to construct factual and counterfactual flood events. This storyline-type attribution method allows investigating the isolated or combined effects of sea level rise and the intensification of cyclone wind speeds on coastal flooding. The results suggest that displacement risk has increased by 3.1 to 3.5% due to the total effects of climate change on coastal flooding, with the effects of increasing wind speed being the dominant factor.
In conclusion, this thesis highlights the potentials and challenges of modeling flood- induced displacement risk. While this work explores the sensitivity of global flood modeling to the choice of input data, new questions arise on how to effectively improve the reproduction of flood return periods and the representation of protection levels. It is also demonstrated that disentangling displacement vulnerabilities is feasible, with the results providing useful information for risk assessments, effective humanitarian aid, and disaster relief. The impact attribution study is a first step in assessing the effects of global warming on displacement risk, leading to new research challenges, e.g., coupling fluvial and coastal flood models or the attribution of other hazard types and displacement events. This thesis is one of the first to address flood-induced displacement risk from a global perspective. The findings motivate for further development of the global flood modeling chain to improve our understanding of displacement vulnerability and the effects of global warming.
The present thesis focuses on the synthesis of nanostructured iron-based compounds by using β-FeOOH nanospindles and poly(ionic liquid)s (PILs) vesicles as hard and soft templates, respectively, to suppress the shuttle effect of lithium polysulfides (LiPSs) in Li-S batteries. Three types of composites with different nanostructures (mesoporous nanospindle, yolk-shell nanospindle, and nanocapsule) have been synthesized and applied as sulfur host material for Li-S batteries. Their interactions with LiPSs and effects on the electrochemical performance of Li-S batteries have been systematically studied.
In the first part of the thesis, carbon-coated mesoporous Fe3O4 (C@M-Fe3O4) nanospindles have been synthesized to suppress the shuttle effect of LiPSs. First, β-FeOOH nanospindles have been synthesized via the hydrolysis of iron (III) chloride in aqueous solution and after silica coating and subsequent calcination, mesoporous Fe2O3 (M-Fe2O3) have been obtained inside the confined silica layer through pyrolysis of β-FeOOH. After the removal of the silica layer, electron tomography (ET) has been applied to rebuild the 3D structure of the M-Fe2O3 nanospindles. After coating a thin layer of polydopamine (PDA) as carbon source, the PDA-coated M-Fe2O3 particles have been calcinated to synthesize C@M-Fe3O4 nanospindles. With the chemisorption of Fe3O4 and confinement of mesoporous structure to anchor LiPSs, the composite C@M-Fe3O4/S electrode delivers a remaining capacity of 507.7 mAh g-1 at 1 C after 600 cycles.
In the second part of the thesis, a series of iron-based compounds (Fe3O4, FeS2, and FeS) with the same yolk-shell nanospindle morphology have been synthesized, which allows for the direct comparison of the effects of compositions on the electrochemical performance of Li-S batteries. The Fe3O4-carbon yolk-shell nanospindles have been synthesized by using the β-FeOOH nanospindles as hard template. Afterwards, Fe3O4-carbon yolk-shell nanospindles have been used as precursors to obtain iron sulfides (FeS and FeS2)-carbon yolk-shell nanospindles through sulfidation at different temperatures. Using the three types of yolk-shell nanospindles as sulfur host, the effects of compositions on interactions with LiPSs and electrochemical performance in Li-S batteries have been systematically investigated and compared. Benefiting from the chemisorption and catalytic effect of FeS2 particles and the physical confinement of the carbon shell, the FeS2-C/S electrode exhibits the best electrochemical performance with an initial specific discharge capacity of 877.6 mAh g-1 at 0.5 C and a retention ratio of 86.7% after 350 cycles.
In the third part, PILs vesicles have been used as soft template to synthesize carbon nanocapsules embedded with iron nitride particles to immobilize and catalyze LiPSs in Li-S batteries. First, 3-n-decyl-1-vinylimidazolium bromide has been used as monomer to synthesize PILs nanovesicles by free radical polymerization. Assisted by PDA coating route and ion exchange, PIL nanovesicles have been successfully applied as soft template in morphology-maintaining carbonization to prepare carbon nanocapsules embedded with iron nitride nanoparticles (FexN@C). The well-dispersed iron nitride nanoparticles effectively catalyze the conversion of LiPSs to Li2S, owing to their high electrical conductivity and strong chemical binding to LiPSs. The constructed FexN@C/S cathode demonstrates a high initial discharge capacity of 1085.0 mAh g-1 at 0.5 C with a remaining value of 930.0 mAh g-1 after 200 cycles.
The results in the present thesis demonstrate the facile synthetic routes of nanostructured iron-based compounds with controllable morphologies and compositions using soft and hard colloidal templates, which can be applied as sulfur host to suppress the shuttle behavior of LiPSs. The synthesis approaches developed in this thesis are also applicable to fabricating other transition metal-based compounds with porous nanostructures for other applications.
Reflexion und Reflexivität
(2023)
Reflexion gilt in der Lehrkräftebildung als eine Schlüsselkategorie der professionellen Entwicklung. Entsprechend wird auf vielfältige Weise die Qualität reflexionsbezogener Kompetenzen untersucht. Eine Herausforderung hierbei kann in der Annahme bestehen, von der Analyse schriftlicher Reflexionen unmittelbar auf die Reflexivität einer Person zu schließen, da Reflexion stets kontextspezifisch als Abbild reflexionsbezogener Argumentationsprozesse angesehen werden sollte und reflexionsbezogenen Dispositionen unterliegt. Auch kann die Qualität einer Reflexion auf mehreren Dimensionen bewertet werden, ohne quantifizierbare, absolute Aussagen treffen zu können.
Daher wurden im Rahmen einer Physik-Videovignette N = 134 schriftliche Fremdreflexionen verfasst und kontextspezifische reflexionsbezogene Dispositionen erhoben. Expert*innen erstellten theoriegeleitet Qualitätsbewertungen zur Breite, Tiefe, Kohärenz und Spezifität eines jeden Reflexionstextes. Unter Verwendung computerbasierter Klassifikations- und Analyseverfahren wurden weitere Textmerkmale erhoben. Mittels explorativer Faktorenanalyse konnten die Faktoren Qualität, Quantität und Deskriptivität gefunden werden. Da alle konventionell eingeschätzten Qualitätsbewertungen durch einen Faktor repräsentiert wurden, konnte ein maximales Qualitätskorrelat kalkuliert werden, zu welchem jede schriftliche Fremdreflexion im Rahmen der vorliegenden Vignette eine computerbasiert bestimmbare Distanz aufweist. Diese Distanz zum maximalen Qualitätskorrelat konnte validiert werden und kann die Qualität der schriftlichen Reflexionen unabhängig von menschlichen Ressourcen quantifiziert repräsentieren. Abschließend konnte identifiziert werden, dass ausgewählte Dispositionen in unterschiedlichem Maße mit der Reflexionsqualität zusammenhängen. So konnten beispielsweise bezogen auf das Physik-Fachwissen minimale Zusammenhänge identifiziert werden, wohingegen Werthaltung sowie wahrgenommene Unterrichtsqualität eng mit der Qualität einer schriftlichen Reflexion in Verbindung stehen können.
Es wird geschlussfolgert, dass reflexionsbezogene Dispositionen moderierenden Einfluss auf Reflexionen nehmen können. Es wird empfohlen bei der Erhebung von Reflexion mit dem Ziel der Kompetenzmessung ausgewählte Dispositionen mit zu erheben. Weiter verdeutlicht diese Arbeit die Möglichkeit, aussagekräftige Quantifizierungen auch in der Analyse komplexer Konstrukte vorzunehmen. Durch computerbasierte Qualitätsabschätzungen können objektive und individuelle Analysen und differenzierteres automatisiertes Feedback ermöglicht werden.
Hegels Phantasie
(2023)
Als »Zwischenreich«, »Drittes« oder »Mitte« bezeichnet, kommt der Imagination seit ihren Anfängen in der Antike die Rolle eines Mediums zu. Gleichzeitig bleibt ihr medialer Aspekt durchgehend ambivalent und prekär. Es ist Georg Wilhelm Friedrich Hegel, der die Imagination nicht mehr als subjektives Vermögen versteht, sondern als Kraft der »Entäußerung« und sie somit medial denkt. In einer bislang wenig beachteten Passage aus Hegels dritter Enzyklopädie von 1830 legt Ekaterina Vassilevski nicht nur die implizite Medialität der Imagination frei, sondern auch den in Hegels Denken verborgenen Begriff des Medialen.
Background: The concept self-compassion (SC), a special way of being compassionate with oneself while dealing with stressful life circumstances, has attracted increasing attention in research over the past two decades. Research has already shown that SC has beneficial effects on affective well-being and other mental health outcomes. However, little is known in which ways SC might facilitate our affective well-being in stressful situations. Hence, a central concern of this dissertation was to focus on the question which underlying processes might influence the link between SC and affective well-being. Two established components in stress processing, which might also play an important role in this context, could be the amount of experienced stress and the way of coping with a stressor. Thus, using a multi-method approach, this dissertation aimed at finding to which extent SC might help to alleviate the experienced stress and promotes the use of more salutary coping, while dealing with stressful circumstances. These processes might ultimately help improve one’s affective well-being. Derived from that, it was hypothesized that more SC is linked to less perceived stress and intensified use of salutary coping responses. Additionally, it was suggested that perceived stress and coping mediate the relation between SC and affective well-being.
Method: The research questions were targeted in three single studies and one meta-study. To test my assumptions about the relations of SC and coping in particular, a systematic literature search was conducted resulting in k = 136 samples with an overall sample size of N = 38,913. To integrate the z-transformed Pearson correlation coefficients, random-effects models were calculated. All hypotheses were tested with a three-wave cross-lagged design in two short-term longitudinal online studies assessing SC, perceived stress and coping responses in all waves. The first study explored the assumptions in a student sample (N = 684) with a mean age of 27.91 years over a six-week period, whereas the measurements were implemented in the GESIS Panel (N = 2934) with a mean age of 52.76 years analyzing the hypotheses in a populationbased sample across eight weeks. Finally, an ambulatory assessment study was designed to expand the findings of the longitudinal studies to the intraindividual level. Thus, a sample of 213 participants completed questionnaires of momentary SC, perceived stress, engagement and disengagement coping, and affective well-being on their smartphones three times per day over seven consecutive days. The data was processed using 1-1-1 multilevel mediation analyses.
Results: Results of the meta-analysis indicated that higher SC is significantly associated with more use of engagement coping and less use of disengagement coping. Considering the relations between SC and stress processing variables in all three single studies, cross-lagged paths from the longitudinal data, as well as multilevel modeling paths from the ambulatory assessment data indicated a notable relation between all relevant stress variables. As expected, results showed a significant negative relation between SC and perceived stress and disengagement coping, as well as a positive connection with engagement coping responses at the dispositional and intra-individual level. However, considering the mediational hypothesis, the most promising pathway in the link between SC and affective well-being turned out to be perceived stress in all three studies, while effects of the mediational pathways through coping responses were less robust.
Conclusion: Thus, a more self-compassionate attitude and higher momentary SC, when needed in specific situations, can help to engage in effective stress processing. Considering the underlying mechanisms in the link between SC and affective well-being, stress perception in particular seemed to be the most promising candidate for enhancing affective well-being at the dispositional and at the intraindividual level. Future research should explore the pathways between SC and affective well-being in specific contexts and samples, and also take into account additional influential factors.
The purpose of this thesis was to investigate the developmental dynamics between interest, motivation, and learning strategy use during physics learning. The target population was lower secondary school students from a developing country, given that there is hardly in research that studies the above domain-specific concepts in the context of developing countries. The aim was addressed in four parts.
The first part of the study was guided by three objectives: (a) to adapt and validate the Science Motivation Questionnaire (SMQ-II) for the Ugandan context; (b) to examine whether there are significant differences in motivation for learning Physics with respect to students’ gender; and (c) to establish the extent to which students’ interest predicts their motivation to learn Physics. Being a pilot study, the sample comprised 374 randomly selected students from five schools in central Uganda who responded to anonymous questionnaires that included scales from the SMQ-II and the Individual Interest Questionnaire. Data were analysed using confirmatory factor analyses, t-tests and structural equation modelling in SPSS-25 and Mplus-8. The five-factor model solution of the SMQ-II fitted adequately with the study data, with deletion of one item. The modified SMQ-II exhibited invariant factor loadings and intercepts (i.e., strong measurement invariance) when administered to boys and girls. Furthermore, on assessing whether motivation for learning Physics varied with gender, no significant differences were noted. On assessing the predictive effects of individual interest on students’ motivation, individual interest significantly predicted all motivational constructs, with stronger predictive strength on students’ self-efficacy and self-determination in learning Physics.
In the second part whilst using comprised 934 Grade 9 students from eight secondary schools in Uganda, Latent profile analysis (LPA) - a person-centred approach was used to investigate motivation patterns that exist in lower secondary school students during physics learning. A three-step approach to LPA was used to answer three research questions: RQ1, which profiles of secondary school students exist with regards to their motivation for Physics learning; RQ2, are there differences in students’ cognitive learning strategies in the identified profiles; and RQ3, does students’ gender, attitudes, and individual interest predict membership in these profiles? Six motivational profiles were identified: (i) low-quantity motivation profile (101 students; 10.8%); (ii) moderate-quantity motivation profile (246 students; 26.3%); (iii) high-quantity motivation profile (365 students; 39.1%); (iv) primarily intrinsically motivated profile (60 students,6.4%); (v) mostly extrinsically motivated profile (88 students, 9.4%); and (vi) grade-introjected profile (74 students, 7.9%). Low-quantity and grade introjected motivated students mostly used surface learning strategies whilst the high-quantity and primarily intrinsically motivated students used deep learning strategies. On examining the predictive effect of gender, individual interest, and students’ attitudes on the profile membership, unlike gender, individual interest and students’ attitudes towards Physics learning strongly predicted profile membership.
In the third part of the study, the occurrence of different secondary school learner profiles depending on their various combinations of cognitive and metacognitive learning strategy use, as well as their differences in perceived autonomy support, intrinsic motivation, and gender was examined. Data were collected from 576 9th grade student. Four learner profiles were identified: competent strategy user, struggling user, surface-level learner, and deep-level learner profiles. Gender differences were noted in students’ use of elaboration and organization strategies to learn Physics, in favour of girls. In terms of profile memberships, significant differences in gender, intrinsic motivation and perceived autonomy support were also noted. Girls were 2.4 - 2.7 times more likely than boys to be members of the competent strategy user and surface-level learner profiles. Additionally, higher levels of intrinsic motivation predicted an increased likelihood membership into the deep-level learner profile, whilst higher levels of perceived teacher autonomy predicted an increased likelihood membership into the competent strategy user profile as compared to other profiles.
Lastly, in the fourth part, changes in secondary school students’ physics motivation and cognitive learning strategies use during physics learning across time were examined. Two waves of data were collected from initially 954 9th students through to their 10th grade. A three-step approach to Latent transition analysis was used. Generally, students’ motivation decreased from 9th to 10th grade. Qualitative students’ motivation profiles indicated strong with-in person stability whilst the quantitative profiles were relatively less stable. Mostly, students moved from the high quantity motivation profile to the extrinsically motivated profiles. On the other hand, the cognitive learning strategies use profiles were moderately stable; with higher with-in person stability in the deep-level learner profile. None of the struggling users and surface-level learners transitioned into the deep-level learners’ profile. Additionally, students who perceived increased support for autonomy from their teachers had higher membership likelihood into the competent users’ profiles whilst those with an increase in individual interest score had higher membership likelihood into the deep-level learner profile.
The increasing global population has led to a growing demand for cost-effective and eco-friendly methods of water purification. This demand has reached a peak due to the increasing presence of impurities and pollutants in water and a growing awareness of waterborne diseases. Advanced oxidation processes (AOPs) are effective methods to address these challenges, due to the generation of highly reactive radicals, such as sulfate radical (SO4•-), hydroxyl radical (•OH), and/or superoxide radical (•O2-) in oxidation reactions. Relative to conventional hydrogen peroxide (H2O2)-based AOPs for wastewater treatment, the persulfate-related AOPs are receiving increasing attention over the past decades, due to their stronger oxidizing capability and a wider pH working window. Further deployment of the seemingly plausible technology as an alternative for the well-established one in industry, however, necessitates a careful evaluation of compounding factors, such as water matrix effects, toxicological consequences, costs, and engineering challenges, etc. To this end, rational design of efficient and environmentally friendly catalysts constitutes an indispensable pathway to advance persulfate activation efficacy and to elucidate the mechanisms in AOPs, the combined endeavors are expected to provide insightful understanding and guidelines for future studies in wastewater treatment. A dozens of transition metal-based catalysts have been developed for persulfate-related AOPs, while the undesirable metal leaching and poor stability in acidic conditions have been identified as major obstacles. Comparatively, the carbonaceous materials are emerging as alternative candidates, which are characterized by metal-free nature, wide availability, and exceptional resistance to acid and alkali, as well as tunable physicochemical and electronic properties, the combined merits make them an attractive option to overcome the aforementioned limitations in metal-based catalytic systems. This dissertation aims at developing novel carbonaceous materials to boost the activity in peroxymonosulfate (PMS) activation processes. Functionalized carbon materials with metal particles or heteroatoms were constructed and further evaluated in terms of their ability to activate PMS for AOPs. The main contents of this thesis are summarized as follows: (1) Iron oxide-loaded biochar: improving stability and alleviating metal leakage Metal leaching constitutes one of the main drawbacks in using transition metals as PMS activators, which is accompanied by the generation of metal-containing sludge, potentially leading to secondary pollution. Meanwhile, the metal nanoparticles are prone to aggregate, causing rapid decay of catalytic performance. The use of carbons as supports for transition metals could mitigate these deficiencies, because the interaction between metals and carbons could in turn disperse and stabilize metal nanoparticles, thus suppressing the metal leaching. In this work, the environmentally benign lignin with its abundant phenolic groups, which is well known to serve as carbon source with high yields and flexibility, was utilized to load Fe ions. The facile low-temperature pre-treatment pyrolytic strategy was employed to construct a green catalyst with iron oxides embedded in Kraft-lignin-derived biochar (termed as γ-Fe2O3@KC). The γ-Fe2O3@KC was capable of activating PMS to generate stable non-radical species (1O2 and Fe (V)=O) and to enhance electron transfer efficiency. A surface-bound reactive complex (catalyst-PMS*) was identified by electrochemical characterizations and discussed with primary surface-bound radical pairs to explain the contradictions between quenching and EPR detection results. The system also showed encouraging reusability for at least 5 times and high stability at pH 3-9. The low concentration of iron in γ-Fe2O3@KC/PMS system implied that the carbon scaffold of biochar substantially alleviated metal leakage. (2) MOF-derived nanocarbon: new carbon crystals Traditional carbon materials are of rather moderate performance in activation PMS, due to the poor electron transfer capacity within the amorphous structure and limited active sites for PMS adsorption. Herein, we established crystalline nanocarbon materials via a simple NaCl-templated strategy using the monoclinic zeolitic imidazolate framework-8 (ZIF-8) sealed with NaCl crystals as the precursors. Specifically, NaCl captured dual advantages in serving as structure-directing agent during hydrolysis and protective salt reactor to facilitate phase transformation during carbonization. The structure-directing agent NaCl provided a protective and confined space for the evolution of MOF upon carbonization, which led to high doping amounts of nitrogen (N) and oxygen elements (O) in carbon framework (N: 14.16 wt%, O: 9.6 wt%) after calcination at a high temperature of 950 oC. We found that N-O co-doping can activate the chemically inert carbon network and the nearby sp2-hybridized carbon atoms served as active sites for adsorption and activation. Besides, the highly crystallized structure with well-established carbon channels around activated carbon atoms could significantly accelerate electron transfer process after initial adsorption of PMS. As such, this crystalline nanocarbon exhibited excellent catalytic kinetics for various pollutants. (3) MOF-derived 2D carbon layers: enhanced mass/electron transfer The two-dimensional (2D) configuration of carbon-based nanosheets with inherent nanochannels and abundant active sites residing on the layer edges or in between the layers, allowed the accessible interaction and close contact between the substrates and reactants, as well as the dramatically improved electron- and mass-transfer kinetics. In this regard, we developed dual-templating strategy to afford 2D assembly of the crystalline carbons, which found efficiency in reinforcing the interactions between the catalyst surface and foreign pollutants. Specifically, we found that the ice crystals and NaCl promoted the evolution of MOF in a 2D fashion during the freezing casting stage, while the later further allowed the formation of a graphitic surface at high calcination temperature, by virtue of the templating effect of molten salt. Due to the highly retained co-doping amounts, N and O heteroatoms created abundant active sites for PMS activation, the 2D configuration of carbon-based nanosheets enable efficient interaction of PMS and pollutants on the surface, which further boosted the kinetics of degradation.
Development of electrochemical antibody-based and enzymatic assays for mycotoxin analysis in food
(2023)
Electrochemical methods are promising to meet the demand for easy-to-use devices monitoring key parameters in the food industry. Many companies run own lab procedures for mycotoxin analysis, but it is a major goal to simplify the analysis. The enzyme-linked immunosorbent assay using horseradish peroxidase as enzymatic label, together with 3,3',5,5' tetramethylbenzidine (TMB)/H2O2 as substrates allows sensitive mycotoxin detection with optical detection methods. For the miniaturization of the detection step, an electrochemical system for mycotoxin analysis was developed. To this end, the electrochemical detection of TMB was studied by cyclic voltammetry on different screen-printed electrodes (carbon and gold) and at different pH values (pH 1 and pH 4). A stable electrode reaction, which is the basis for the further construction of the electrochemical detection system, could be achieved at pH 1 on gold electrodes. An amperometric detection method for oxidized TMB, using a custom-made flow cell for screen-printed electrodes, was established and applied for a competitive magnetic bead-based immunoassay for the mycotoxin ochratoxin A. A limit of detection of 150 pM (60 ng/L) could be obtained and the results were verified with optical detection. The applicability of the magnetic bead-based immunoassay was tested in spiked beer using a handheld potentiostat connected via Bluetooth to a smartphone for amperometric detection allowing to quantify ochratoxin A down to 1.2 nM (0.5 µg/L).
Based on the developed electrochemical detection system for TMB, the applicability of the approach was demonstrated with a magnetic bead-based immunoassay for the ergot alkaloid, ergometrine. Under optimized assay conditions a limit of detection of 3 nM (1 µg/L) was achieved and in spiked rye flour samples ergometrine levels in a range from 25 to 250 µg/kg could be quantified. All results were verified with optical detection. The developed electrochemical detection method for TMB gives great promise for the detection of TMB in many other HRP-based assays.
A new sensing approach, based on an enzymatic electrochemical detection system for the mycotoxin fumonisin B1 was established using an Aspergillus niger fumonisin amine oxidase (AnFAO). AnFAO was produced recombinantly in E. coli as maltose-binding protein fusion protein and catalyzes the oxidative deamination of fumonisins, producing hydrogen peroxide. It was found that AnFAO has a high storage and temperature stability. The enzyme was coupled covalently to magnetic particles, and the enzymatically produced H2O2 in the reaction with fumonisin B1 was detected amperometrically in a flow injection system using Prussian blue/carbon electrodes and the custom-made wall-jet flow cell. Fumonisin B1 could be quantified down to 1.5 µM (≈ 1 mg/L). The developed system represents a new approach to detect mycotoxins using enzymes and electrochemical methods.
This research focuses on empowering leadership, a leadership style that shares autonomy and responsibilities with the followers. Empowering leadership enhances the meaningfulness of work by fostering participation in decision-making, expressing confidence in high performance, and providing autonomy in target setting (Cheong, 2016). I examine how empowering leadership affects followers’ reflection. I used data from 528 individuals across 172 teams and found a positive relationship between empowering leadership and followers’ reflection. Followers’ reflection, in turn, is negatively associated with followers’ withdrawal, which mediates the beneficial effect of empowering leadership on leaders’ emotional exhaustion. As for the leaders, I propose that empowering leadership is negatively related also to leaders’ emotional exhaustion. This research broadens our understanding of empowering leadership's effects on both followers and leaders. Moreover, it integrates empowering leadership, leader emotional exhaustion, and burnout literature. Overall, empowering leadership strengthens members’ reflective attitudes and behaviors, which result in reduced withdrawal (and increased presence and contribution) in teams. Because the members contribute to team effort more, the leaders experience less emotional exhaustion. Hence, my work not only identifies new ways through which empowering leadership positively affects followers but also shows how these positive effects on followers benefit the leaders’ well-being.
In dieser Dissertation konnten erfolgreich mechanisch stabile Hydrogele über eine freie radikalische Polymerisation (FRP) in Wasser synthetisiert werden. Dabei diente vor allem das Sulfobetain SPE als Monomer. Dieses wurde mit dem über eine nukleophile Substitution erster bzw. zweiter Ordnung hergestellten Vernetzer TMBEMPA/Br umgesetzt.
Die entstandenen Netzwerke wurden im Gleichgewichtsquellzustand im Wesentlichen mittels Niederfeld-Kernresonanzspektroskopie, Röntgenkleinwinkelstreuung (SAXS), Rasterelektronenmikroskopie mit Tieftemperaturtechnik (Kryo-REM), dynamisch-mechanische Analyse (DMA), Rheologie, thermogravimetrische Analyse (TGA) und dynamische Differenzkalorimetrie (DSC) analysiert.
Das hierarchisch aufgebaute Netzwerk wurde anschließend für die matrixgesteuerten Mineralisation von Calciumphosphat und –carbonat genutzt. Über das alternierende Eintauchverfahren (engl. „alternate soaking method“) und der Variation von Mineralisationsparametern, wie pH-Wert, Konzentration c und Temperatur T konnten dann verschiedene Modifikationen des Calciumphosphats generiert werden. Das entstandene Hybridmaterial wurde qualitativ mittels Röntgenpulverdiffraktometrie (XRD), abgeschwächte Totalreflexion–fouriertransformierte Infrarot Spektroskopie (ATR-FTIR), Raman-Spektroskopie, Rasterelektronenmikroskopie (REM) mit energiedispersiver Röntgenspektroskopie (EDXS) und optischer Mikroskopie (OM) als auch quantitative mittels Gravimetrie und TGA analysiert.
Für die potentielle Verwendung in der Medizintechnik, z.B. als Implantatmaterial, ist die grundlegende Einschätzung der Wechselwirkung zwischen Hydrogel bzw. Hybridmaterial und verschiedener Zelltypen unerlässlich. Dazu wurden verschiedene Zelltypen, wie Einzeller, Bakterien und adulte Stammzellen verwendet. Die Wechselwirkung mit Peptidsequenzen von Phagen komplettiert das biologische Unterkapitel.
Hydrogele sind mannigfaltig einsetzbar. Diese Arbeit fasst daher weitere Projektperspektiven, auch außerhalb des biomedizinischem Anwendungsspektrums, auf. So konnten erste Ansätze zur serienmäßige bzw. maßgeschneiderte Produktion über das „Inkjet“ Verfahren erreicht werden. Um dies ermöglichen zu können wurden erfolgreich weitere Synthesestrategien, wie die Photopolymerisation und die redoxinitiierte Polymerisation, ausgenutzt. Auch die Eignung als Filtermaterial oder Superabsorber wurde analysiert.
Establishment of final leaf size in plants represents a complex mechanism that relies on the precise regulation of two interconnected cellular processes, cell division and cell expansion. In previous work, the barley protein BROAD LEAF1 (BLF1) was identified as a novel negative regulator of cell proliferation, that mainly limits leaf growth in the width direction. Here I identified a novel RING/U-box protein that interacts with BLF1 through a yeast two hybrid screen. Using BiFC, Co-IP and FRET I confirmed the interaction of the two proteins in planta. Enrichment of the BLF1-mEGFP fusion protein and the increase of the FRET signal upon MG132 treatment of tobacco plants, together with an in vivo ubiquitylation assay in bacteria, confirmed that the RING/U-box E3 interacts with BLF1 to mediate its ubiquitylation and degradation by the 26S proteasome system. Consistent with regulation of endogenous BLF1 in barley by proteasomal degradation, inhibition of the proteasome by bortezomib treatment on BLF1-vYFP transgenic barley plants also resulted in an enrichment of the BLF1 protein. I thus demonstrated that RING/U-box E3 is colocalized with BLF1 in nuclei and negatively regulates BLF1 protein levels. Analysis of ring-e3_1 knock-out mutants suggested the involvement of the RING/U-box E3 gene in leaf growth control, although the effect was mainly on leaf length. Together, my results suggest that proteasomal degradation, possibly mediated by RING/U-box E3, contributes to fine-tuning BLF1 protein-level in barley.
Deutsche Blauhelme in Afrika
(2023)
Warum trat die Bundesregierung ab Ende der 1980er Jahre weltweit als sicherheitspolitischer Akteur in Erscheinung? Warum engagierte sie sich in multinationalen Missionen der Vereinten Nationen etwa in Somalia, Namibia und Ruanda mit Soldaten oder Polizisten - und in anderen Missionen in Afrika im gleichen Zeitraum nicht? Gestützt auf ministerielle Archivquellen untersucht Torsten Konopka die Prozesse der nationalen Entscheidungsfindung, die zu einer Beteiligung oder Nichtbeteiligung an VN-Missionen in Afrika führten. Das Buch leistet einen politik- sowie militärgeschichtlichen Beitrag zur Genese der frühen Auslandsverwendungen der Bundeswehr.
An exploration of activity and therapist preferences and their predictors in German-speaking samples
(2023)
According to current definitions of evidence-based practice, patients’ preferences play an important role for the psychotherapeutic process and outcomes. However, whereas a significant body of research investigated preferences regarding specific treatments, research on preferred activities or therapist characteristics is rare, investigated heterogeneous aspects with inconclusive results, lacked validated assessment tools, and neglected relevant preferences, their predictors as well as the perspective of mental health professionals. Therefore, the three studies of this dissertation aimed to address the most fundamental drawbacks in current preference research by providing a validated questionnaire, focus efforts on activity and therapist preferences and add preferences of psychotherapy trainees. To this end, Paper I reports the translation and validation of the 18-item Cooper-Norcross Inventory of Preference (C-NIP) in a broad, heterogeneous sample of N = 969 laypeople, resulting in good to acceptable reliabilities and first evidence of validity. However, the original factor structure was not replicated. Paper II assesses activity preferences of psychotherapists in training using the C-NIP and compares them with the initial laypeople sample. There were significant differences between both samples, with trainees preferring a more patient-directed, emotionally intense and confrontational approach than laypeople. CBT trainees preferred a more therapist-directed, present-focused, challenging and less emotional intense approach than psychodynamic or -analytic trainees. Paper III explores therapist preferences and tests predictors for specific preference choices. For most characteristics, more than half of the participants did not have specific preferences. Results pointed towards congruency effects (i.e., preference for similar characteristics), especially for members of marginalized groups. The dissertation provides both researchers and practitioners with a validated questionnaire, shows potentially obstructive differences between patients and therapists and underlines the importance of therapist characteristics for marginalized groups, thereby laying the foundation for future applications and implementations in research and practice.
Aging is a complex process characterized by several factors, including loss of genetic and epigenetic information, accumulation of chronic oxidative stress, protein damage and aggregates and it is becoming an emergent drug target. Therefore, it is the utmost importance to study aging and agerelated diseases, to provide treatments to develop a healthy aging process. Skeletal muscle is one of the earliest tissues affected by age-related changes with progressive loss of muscle mass and function from 30 years old, effect known as sarcopenia. Several studies have shown the accumulation of protein aggregates in different animal models, as well as in humans, suggesting impaired proteostasis, a hallmark of aging, especially regarding degradation systems. Thus, different publications have explored the role of the main proteolytic systems in skeletal muscle from rodents and humans, like ubiquitin proteasomal system (UPS) and autophagy lysosomal system (ALS), however with contradictory results. Yet, most of the published studies are performed in muscles that comprise more than one fiber type, that means, muscles composed by slow and fast fibers. These fiber types, exhibit different metabolism and contraction speed; the slow fibers or type I display an oxidative metabolism, while fast fibers function towards a glycolytic metabolism ranging from fast oxidative to fast glycolytic fibers. To this extent, the aim of this thesis sought to understand on how aging impacts both fiber types not only regarding proteostasis but also at a metabolome and transcriptome network levels. Therefore, the first part of this thesis, presents the differences between slow oxidative (from Soleus muscle) and fast glycolytic fibers (Extensor digitorum longus, EDL) in terms of degradation systems and how they cope with oxidative stress during aging, while the second part explores the differences between young and old EDL muscle transcriptome and metabolome, unraveling molecular features. More specifically, the results from the present work show that slow oxidative muscle performs better at maintaining the function of UPS and ALS during aging than EDL muscle, which is clearly affected, accounting for the decline in the catalytic activity rates and accumulation of autophagy-related proteins. Strinkingly, transcriptome and metabolome analyses reveal that fast glycolytic muscle evidences significant downregulation of mitochondrial related processes and damaged mitochondria morphology during aging, despite of having a lower oxidative metabolism compared to oxidative fibers. Moreover, predictive analyses reveal a negative association between aged EDL gene signature and lifespan extending interventions such as caloric restriction (CR). Although, CR intervention does not alter the levels of mitochondrial markers in aged EDL muscle, it can reverse the higher mRNA levels of muscle damage markers. Together, the results from this thesis give new insights about how different metabolic muscle fibers cope with age-related changes and why fast glycolytic fibers are more susceptible to aging than slow oxidative fibers.
Fördern und Zensieren
(2023)
»European Environmental Law and its Influence on Grandfathering – a Limiting Factor?«: How to deal with conflicts that arise between legally permitted activities and nature despite prior comprehensive environmental assessments? The author examines this question regarding EU species, habitat protection and environmental damage law. The material EU environmental law requirements for the use of permits are outlined, as well as the administrative instruments for their enforcement. A differentiation is made between permits under the Federal Immission Control Act and plan approvals.
Evaluation of nitrogen dynamics in high-order streams and rivers based on high-frequency monitoring
(2023)
Nutrient storage, transform and transport are important processes for achieving environmental and ecological health, as well as conducting water management plans. Nitrogen is one of the most noticeable elements due to its impacts on tremendous consequences of eutrophication in aquatic systems. Among all nitrogen components, researches on nitrate are blooming because of widespread deployments of in-situ high-frequency sensors. Monitoring and studying nitrate can become a paradigm for any other reactive substances that may damage environmental conditions and cause economic losses.
Identifying nitrate storage and its transport within a catchment are inspiring to the management of agricultural activities and municipal planning. Storm events are periods when hydrological dynamics activate the exchange between nitrate storage and flow pathways. In this dissertation, long-term high-frequency monitoring data at three gauging stations in the Selke river were used to quantify event-scale nitrate concentration-discharge (C-Q) hysteretic relationships. The Selke catchment is characterized into three nested subcatchments by heterogeneous physiographic conditions and land use. With quantified hysteresis indices, impacts of seasonality and landscape gradients on C-Q relationships are explored. For example, arable area has deep nitrate legacy and can be activated with high intensity precipitation during wetting/wet periods (i.e., the strong hydrological connectivity). Hence, specific shapes of C-Q relationships in river networks can identify targeted locations and periods for agricultural management actions within the catchment to decrease nitrate output into downstream aquatic systems like the ocean.
The capacity of streams for removing nitrate is of both scientific and social interest, which makes the quantification motivated. Although measurements of nitrate dynamics are advanced compared to other substances, the methodology to directly quantify nitrate uptake pathways is still limited spatiotemporally. The major problem is the complex convolution of hydrological and biogeochemical processes, which limits in-situ measurements (e.g., isotope addition) usually to small streams with steady flow conditions. This makes the extrapolation of nitrate dynamics to large streams highly uncertain. Hence, understanding of in-stream nitrate dynamic in large rivers is still necessary. High-frequency monitoring of nitrate mass balance between upstream and downstream measurement sites can quantitatively disentangle multi-path nitrate uptake dynamics at the reach scale (3-8 km). In this dissertation, we conducted this approach in large stream reaches with varying hydro-morphological and environmental conditions for several periods, confirming its success in disentangling nitrate uptake pathways and their temporal dynamics. Net nitrate uptake, autotrophic assimilation and heterotrophic uptake were disentangled, as well as their various diel and seasonal patterns. Natural streams generally can remove more nitrate under similar environmental conditions and heterotrophic uptake becomes dominant during post-wet seasons. Such two-station monitoring provided novel insights into reach-scale nitrate uptake processes in large streams.
Long-term in-stream nitrate dynamics can also be evaluated with the application of water quality model. This is among the first time to use a data-model fusion approach to upscale the two-station methodology in large-streams with complex flow dynamics under long-term high-frequency monitoring, assessing the in-stream nitrate retention and its responses to drought disturbances from seasonal to sub-daily scale. Nitrate retention (both net uptake and net release) exhibited substantial seasonality, which also differed in the investigated normal and drought years. In the normal years, winter and early spring seasons exhibited extensive net releases, then general net uptake occurred after the annual high-flow season at later spring and early summer with autotrophic processes dominating and during later summer-autumn low-flow periods with heterotrophy-characteristics predominating. Net nitrate release occurred since late autumn until the next early spring. In the drought years, the late-autumn net releases were not so consistently persisted as in the normal years and the predominance of autotrophic processes occurred across seasons. Aforementioned comprehensive results of nitrate dynamics on stream scale facilitate the understanding of instream processes, as well as raise the importance of scientific monitoring schemes for hydrology and water quality parameters.
Planets outside our solar system, so-called "exoplanets", can be detected with different methods, and currently more than 5000 exoplanets have been confirmed, according to NASA Exoplanet Archive. One major highlight of the studies on exoplanets in the past twenty years is the characterization of their atmospheres usingtransmission spectroscopy as the exoplanet transits. However, this characterization is a challenging process and sometimes there are reported discrepancies in the literature regarding the atmosphere of the same exoplanet. One potential reason for the observed atmospheric inconsistencies is called impact parameter degeneracy, and it is highly driven by the limb darkening effect of the host star. A brief introductionto those topics in presented in chapter 1, while the motivation and objectives of thiswork are described in chapter 2.The first goal is to clarify the origin of the transmission spectrum, which is anindicator of an exoplanet’s atmosphere; whether it is real or influenced by the impactparameter degeneracy. A second goal is to determine whether photometry from space using the Transiting Exoplanet Survey Satellite (TESS), could improve on the major parameters, which are responsible for the aforementioned degeneracy, of known exoplanetary systems. Three individual projects were conducted in order toaddress those goals. The three manuscripts are presented, in short, in the manuscriptoverview in chapter 3.More specifically, in chapter 4, the first manuscript is presented, which is an ex-tended investigation on the impact parameter degeneracy and its application onsynthetic transmission spectra. Evidently, the limb darkening of the host star isan important driver for this effect. It keeps the degeneracy persisting through different groups of exoplanets, based on the uncertainty of their impact parameter and on the type of their host star. The second goal, was addressed in the second and third manuscripts (chapter 5 and chapter 6 respectively). Using observationsfrom the TESS mission, two samples of exoplanets were studied; 10 transiting inflated hot-Jupiters and 43 transiting grazing systems. Potentially, the refinement or confirmation of their major system parameters’ measurements can assist in solving current or future discrepancies regarding their atmospheric characterization.In chapter 7 the conclusions of this work are discussed, while in chapter 8 itis proposed how TESS’s measurements can be able to discern between erroneousinterpretations of transmission spectra, especially on systems where the impact parameter degeneracy is likely not applicable.
Transposable elements (TEs) are loci that can replicate and multiply within the genome of their host. Within the host, TEs through transposition are responsible for variation on genomic architecture and gene regulation across all vertebrates. Genome assemblies have increased in numbers in recent years. However, to explore in deep the variations within different genomes, such as SNPs (single nucleotide polymorphism), INDELs (Insertion-deletion), satellites and transposable elements, we need high-quality genomes. Studies of molecular markers in the past 10 years have limitations to correlate with biological differences because molecular markers rely on the accuracy of the genomic resources. This has generated that a substantial part of the studies of TE in recent years have been on high quality genomic resources such as Drosophila, zebrafinch and maize. As testudine have a slow mutation rate lower only to crocodilians, with more than 300 species, adapted to different environments all across the globe, the testudine clade can help us to study variation. Here we propose Testudines as a clade to study variation and the abundance of TE on different species that diverged a long time ago. We investigated the genomic diversity of sea turtles, identifying key genomic regions associated to gene family duplication, specific expansion of particular TE families for Dermochelyidae and that are important for phenotypic differentiation, the impact of environmental changes on their populations, and the dynamics of TEs within different lineages. In chapter 1, we identify that despite high levels of genome synteny within sea turtles, we identified that regions of reduced collinearity and microchromosomes showed higher concentrations of multicopy gene families, as well as genetic distances between species, indicating their potential importance as sources of variation underlying phenotypic differentiation. We found that differences in the ecological niches occupied by leatherback and green turtles have led to contrasting evolutionary paths for their olfactory receptor genes. We identified in leatherback turtles a long-term low population size. Nonetheless, we identify no correlation between the regions of reduced collinearity with abundance of TEs or an accumulation of a particular TE group. In chapter 2, we identified that sea turtle genomes contain a significant proportion of TEs, with differences in TE abundance between species, and the discovery of a recent expansion of Penelope-like elements (PLEs) in the highly conserved sea turtle genome provides new insights into the dynamics of TEs within Testudines. In chapter 3, we compared the proportion of TE across the Testudine clade, and we identified that the proportion of transposable elements within the clade is stable, regardless of the quality of the assemblies. However, we identified that the proportion of TEs orders has correlation with genome quality depending of their expanded abundancy. For retrotransposon, a highly abundant element for this clade, we identify no correlation. However, for DNA elements a rarer element on this clade, correlate with the quality of the assemblies.
Here we confirm that high-quality genomes are fundamental for the study of transposable element evolution and the conservation within the clade. The detection and abundance of specific orders of TEs are influenced by the quality of the genomes. We identified that a reduction in the population size on D. coriacea had left signals of long-term low population sizes on their genomes. On the same note we identified an expansion of TE on D. coriacea, not present in any other member of the available genomes of Testudines, strongly suggesting that it is a response of deregulation of TE on their genomes as consequences of the low population sizes.
Here we have identified important genomic regions and gene families for phenotypic differentiation and highlighted the impact of environmental changes on the populations of sea turtles. We stated that accurate classification and analysis of TE families are important and require high-quality genome assemblies. Using TE analysis we manage to identify differences in highly syntenic species. These findings have significant implications for conservation and provide a foundation for further research into genome evolution and gene function in turtles and other vertebrates. Overall, this study contributes to our understanding of evolutionary change and adaptation mechanisms.
Distributed decision-making studies the choices made among a group of interactive and self-interested agents. Specifically, this thesis is concerned with the optimal sequence of choices an agent makes as it tries to maximize its achievement on one or multiple objectives in the dynamic environment. The optimization of distributed decision-making is important in many real-life applications, e.g., resource allocation (of products, energy, bandwidth, computing power, etc.) and robotics (heterogeneous agent cooperation on games or tasks), in various fields such as vehicular network, Internet of Things, smart grid, etc.
This thesis proposes three multi-agent reinforcement learning algorithms combined with game-theoretic tools to study strategic interaction between decision makers, using resource allocation in vehicular network as an example. Specifically, the thesis designs an interaction mechanism based on second-price auction, incentivizes the agents to maximize multiple short-term and long-term, individual and system objectives, and simulates a dynamic environment with realistic mobility data to evaluate algorithm performance and study agent behavior.
Theoretical results show that the mechanism has Nash equilibria, is a maximization of social welfare and Pareto optimal allocation of resources in a stationary environment. Empirical results show that in the dynamic environment, our proposed learning algorithms outperform state-of-the-art algorithms in single and multi-objective optimization, and demonstrate very good generalization property in significantly different environments. Specifically, with the long-term multi-objective learning algorithm, we demonstrate that by considering the long-term impact of decisions, as well as by incentivizing the agents with a system fairness reward, the agents achieve better results in both individual and system objectives, even when their objectives are private, randomized, and changing over time. Moreover, the agents show competitive behavior to maximize individual payoff when resource is scarce, and cooperative behavior in achieving a system objective when resource is abundant; they also learn the rules of the game, without prior knowledge, to overcome disadvantages in initial parameters (e.g., a lower budget).
To address practicality concerns, the thesis also provides several computational performance improvement methods, and tests the algorithm in a single-board computer. Results show the feasibility of online training and inference in milliseconds.
There are many potential future topics following this work. 1) The interaction mechanism can be modified into a double-auction, eliminating the auctioneer, resembling a completely distributed, ad hoc network; 2) the objectives are assumed to be independent in this thesis, there may be a more realistic assumption regarding correlation between objectives, such as a hierarchy of objectives; 3) current work limits information-sharing between agents, the setup befits applications with privacy requirements or sparse signaling; by allowing more information-sharing between the agents, the algorithms can be modified for more cooperative scenarios such as robotics.