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In the present work, we study wave phenomena in strongly nonlinear lattices. Such lattices are characterized by the absence of classical linear waves. We demonstrate that compactons – strongly localized solitary waves with tails decaying faster than exponential – exist and that they play a major role in the dynamics of the system under consideration. We investigate compactons in different physical setups. One part deals with lattices of dispersively coupled limit cycle oscillators which find various applications in natural sciences such as Josephson junction arrays or coupled Ginzburg-Landau equations. Another part deals with Hamiltonian lattices. Here, a prominent example in which compactons can be found is the granular chain. In the third part, we study systems which are related to the discrete nonlinear Schrödinger equation describing, for example, coupled optical wave-guides or the dynamics of Bose-Einstein condensates in optical lattices. Our investigations are based on a numerical method to solve the traveling wave equation. This results in a quasi-exact solution (up to numerical errors) which is the compacton. Another ansatz which is employed throughout this work is the quasi-continuous approximation where the lattice is described by a continuous medium. Here, compactons are found analytically, but they are defined on a truly compact support. Remarkably, both ways give similar qualitative and quantitative results. Additionally, we study the dynamical properties of compactons by means of numerical simulation of the lattice equations. Especially, we concentrate on their emergence from physically realizable initial conditions as well as on their stability due to collisions. We show that the collisions are not exactly elastic but that a small part of the energy remains at the location of the collision. In finite lattices, this remaining part will then trigger a multiple scattering process resulting in a chaotic state.
Die gesundheitsfördernden Eigenschaften von grünem Tee sind weitgehend akzeptiert. Den Teecatechinen, insbesondere dem Epigallocatechin-3-gallat (EGCG), werden zahlreiche positive Effekte zugesprochen (z. B. antioxidativ, antikanzerogen, antiinflammatorisch, Blutdruck und Cholesterinspiegel senkend). Die Mechanismen, die zu einer Reduktion der in Tierversuchen beschriebenen Körper- und Fettmasse führen, sind nicht ausreichend geklärt. Ziel dieser Arbeit bestand darin, die kurz- und mittelfristigen Wirkungen einer TEAVIGO®-Applikation (mind. 94 % EGCG) am Mausmodell im Hinblick auf den Energie- und Fettstoffwechsel sowie die Expression daran beteiligter Gene in wichtigen Organen und Geweben zu untersuchen. In verschiedenen Tierversuchen wurde männlichen C57BL/6-Mäusen eine Hochfettdiät (HFD) mit und ohne Supplementation (oral, diätetisch) des entkoffeinierten Grüntee-Extraktes TEAVIGO® in unterschiedlichen Dosierungen gefüttert. Es wurden sowohl kurz- als auch mittelfristige Wirkungen des EGCG auf die Energiebilanz (u. a. indirekte Tierkalorimetrie) und Körperzusammensetzung (NMR) sowie die exogene Substratoxidation (Stabilisotopentechnik: Atemtests, Inkorporation natürlicher 13C-angereicherter Triglyceride aus Maiskeimöl in diverse Organe/Gewebe) und Gen-expression (quantitative real-time PCR) untersucht. Die Applikationsform und ihre Dauer riefen unterschiedliche Wirkungen hervor. Mäuse mit diätetischer Supplementation zeigten bereits nach kurzer Zeit eine verminderte Körperfettmasse, die bei weiterer Verabreichung auch zu einer Reduktion der Körpermasse führte. Beide Applikationsformen resultieren, unabhängig von der Dauer der Intervention, in einer erhöhten Energieausscheidung, während die Futter- und Energieaufnahme durch EGCG nicht beeinflusst wurden. Der Energieverlust war von einer erhöhten Fett- und Stickstoffausscheidung begleitet, deren Ursache die in der Literatur beschriebene Interaktion und Hemmung digestiver Enzyme sein könnte. Besonders unter postprandialen Bedingungen wiesen EGCG-Mäuse erniedrigte Triglycerid- und Glycogengehalte in der Leber auf, was auf eine eingeschränkte intestinale Absorption der Nährstoffe hindeutet. Transkriptanalysen ergaben im Darm eine verminderte Expression von Fettsäuretransportern, während die Expression von Glucosetransportern durch EGCG erhöht wurde. Weiterhin reduzierte EGCG, nach Umstellung von Standard- auf eine maiskeimölhaltige Hochfettdiät, die Inkorporation natürlicher 13C-angereicherter Triglyceride in diverse Organe und Gewebe – insbesondere Leber, viszerales und braunes Fettgewebe sowie Skelettmuskel. Die Analyse der 13C-Anreicherung im Atem der Mäuse und die Energieumsatzmessungen ergaben nach kurzer Applikation eine erhöhte Fettoxidation, die im weiteren Verlauf der Intervention auf eine erhöhte Kohlenhydratoxidation umgeschaltet wurde. Weiterhin war die orale Applikation von EGCG bei gleichzeitiger Fütterung einer Hochfettdiät von makroskopischen und mikroskopischen degenerativen Veränderungen der Leber begleitet. Diese Effekte wurden nach diätetischer Supplementation der Hochfettdiät mit EGCG nicht beobachtet. Zusammenfassend zeigen die Ergebnisse, dass die Körpergewichts- und Fettgewebs-abnahme durch diätetisches EGCG sich durch eine herabgesetzte Verdaulichkeit der Nahrung erklären lässt. Dies führte zu verschiedenen kurz- und mittelfristigen Veränderungen in der Fettverteilung und im Fettmetabolismus.
This thesis is focused on the electronic, spin-dependent and dynamical properties of thin magnetic systems. Photoemission-related techniques are combined with synchrotron radiation to study the spin-dependent properties of these systems in the energy and time domains. In the first part of this thesis, the strength of electron correlation effects in the spin-dependent electronic structure of ferromagnetic bcc Fe(110) and hcp Co(0001) is investigated by means of spin- and angle-resolved photoemission spectroscopy. The experimental results are compared to theoretical calculations within the three-body scattering approximation and within the dynamical mean-field theory, together with one-step model calculations of the photoemission process. From this comparison it is demonstrated that the present state of the art many-body calculations, although improving the description of correlation effects in Fe and Co, give too small mass renormalizations and scattering rates thus demanding more refined many-body theories including nonlocal fluctuations. In the second part, it is shown in detail monitoring by photoelectron spectroscopy how graphene can be grown by chemical vapour deposition on the transition-metal surfaces Ni(111) and Co(0001) and intercalated by a monoatomic layer of Au. For both systems, a linear E(k) dispersion of massless Dirac fermions is observed in the graphene pi-band in the vicinity of the Fermi energy. Spin-resolved photoemission from the graphene pi-band shows that the ferromagnetic polarization of graphene/Ni(111) and graphene/Co(0001) is negligible and that graphene on Ni(111) is after intercalation of Au spin-orbit split by the Rashba effect. In the last part, a time-resolved x-ray magnetic circular dichroic-photoelectron emission microscopy study of a permalloy platelet comprising three cross-tie domain walls is presented. It is shown how a fast picosecond magnetic response in the precessional motion of the magnetization can be induced by means of a laser-excited photoswitch. From a comparision to micromagnetic calculations it is demonstrated that the relatively high precessional frequency observed in the experiments is directly linked to the nature of the vortex/antivortex dynamics and its response to the magnetic perturbation. This includes the time-dependent reversal of the vortex core polarization, a process which is beyond the limit of detection in the present experiments.
Um Prozesse in biologischen Systemen auf molekularer Ebene zu untersuchen, haben sich vor allem fluoreszenzspektroskopische Methoden bewährt. Die Möglichkeit, einzelne Moleküle zu beobachten, hat zu einem deutlichen Fortschritt im Verständnis von elementaren biochemischen Prozessen geführt. Zu einer der bekanntesten Methoden der Einzelmolekülspektroskopie zählt die Fluoreszenz-Korrelations-Spektroskopie (FCS), mit deren Hilfe intramolekulare und diffusionsgesteuerte Prozesse in einem Zeitbereich von µs bis ms untersucht werden können. Durch die Verwendung von sog. Fluoreszenzsonden können Informationen über deren molekulare Mikroumgebung erhalten werden. Insbesondere für die konfokale Mikroskopie und die Einzelmolekülspektroskopie werden Fluoreszenzfarbstoffe mit einer hohen Photostabilität und hohen Fluoreszenzquantenausbeute benötigt. Aufgrund ihrer hohen Fluoreszenzquantenausbeute und der Möglichkeit, maßgeschneiderte“ Farbstoffe in einem breiten Spektralbereich für die Absorption und Fluoreszenz zu entwickeln, sind Cyaninfarbstoffe von besonderem Interesse für bioanalytische Anwendungen. Als Fluoreszenzmarker finden diese Farbstoffe insbesondere in der klinischen Diagnostik und den Lebenswissenschaften Verwendung. Die in dieser Arbeit verwendeten Farbstoffe DY-635 und DY-647 sind zwei typische Vertreter dieser Farbstoffklasse. Durch Modifizierung können die Farbstoffe kovalent an biologisch relevante Moleküle gebunden werden. Aufgrund ihres Absorptionsmaximums oberhalb von 630nm werden sie insbesondere in der Bioanalytik eingesetzt. In der vorliegenden Arbeit wurden die spektroskopischen Eigenschaften der Cyaninfarbstoffe DY-635 und DY-647 in biomimetischen und biologischen Modellsystemen untersucht. Zur Charakterisierung wurden dabei neben der Absorptionsspektroskopie insbesondere fluoreszenzspektroskopische Methoden verwendet. Dazu zählen die zeitkorrelierte Einzelphotonenzählung zur Ermittlung des Fluoreszenzabklingverhaltens, Fluoreszenz-Korrelations-Spektroskopie (FCS) zur Beobachtung von Diffusions- und photophysikalischen Desaktivierungsprozessen und die zeitaufgelöste Fluoreszenzanisotropie zur Untersuchung der Rotationsdynamik und Beweglichkeit der Farbstoffe im jeweiligen Modellsystem. Das Biotin-Streptavidin-System wurde als Modellsystem für die Untersuchung von Protein-Ligand-Wechselwirkungen verwendet, da der Bindungsmechanismus weitgehend aufgeklärt ist. Nach Bindung der Farbstoffe an Streptavidin wurde eine erhebliche Veränderung in den Absorptions- und Fluoreszenzeigenschaften beobachtet. Es wird angenommen, dass diese spektralen Veränderungen durch Wechselwirkung von benachbarten, an ein Streptavidintetramer gebundenen Farbstoffmolekülen und Bildung von H-Dimeren verursacht wird. Für das System Biotin-Streptavidin ist bekannt, dass während der Bindung des Liganden (Biotin) an das Protein eine Konformationsänderung auftritt. Anhand von zeitaufgelösten Fluoreszenzanisotropieuntersuchungen konnte in dieser Arbeit gezeigt werden, dass diese strukturellen Veränderungen zu einer starken Einschränkung der Beweglichkeit des Farbstoffes DY-635B führen. Liegt eine Mischung von ungebundenem und Streptavidin-gebundenem Farbstoff vor, können die Anisotropieabklingkurven nicht nach einem exponentiellen Verlauf angepasst werden. Es konnte im Rahmen dieser Arbeit gezeigt werden, dass in diesem Fall die Auswertung mit Hilfe des Assoziativen Anisotropiemodells möglich ist, welches eine Unterscheidung der Beiträge aus den zwei verschiedenen Mikroumgebungen ermöglicht. Als zweites Modellsystem dieser Arbeit wurden Mizellen des nichtionischen Tensids Tween-20 eingesetzt. Mizellen bilden eines der einfachsten Systeme, um die Mikroumgebung einer biologischen Membran nachzuahmen. Sind die Farbstoffe in den Mizellen eingelagert, so kommt es zu keiner Veränderung der Mizellgröße. Die ermittelten Werte des Diffusionskoeffizienten der mizellar eingelagerten Farbstoffe spiegeln demzufolge die Translationsbewegung der Tween-20-Mizellen wider. Die Beweglichkeit der Farbstoffe innerhalb der Tween-20-Mizellen wurde durch zeitaufgelöste Fluoreszenzanisotropiemessungen untersucht. Neben der „Wackelbewegung“, entsprechend dem wobble-in-a-cone-Modell, wird zusätzlich noch die laterale Diffusion der Farbstoffe entlang der Mizelloberfläche beschrieben.
Preparation and investigation of polymer-foam films and polymer-layer systems for ferroelectrets
(2010)
Piezoelectric materials are very useful for applications in sensors and actuators. In addition to traditional ferroelectric ceramics and ferroelectric polymers, ferroelectrets have recently become a new group of piezoelectrics. Ferroelectrets are functional polymer systems for electromechanical transduction, with elastically heterogeneous cellular structures and internal quasi-permanent dipole moments. The piezoelectricity of ferroelectrets stems from linear changes of the dipole moments in response to external mechanical or electrical stress. Over the past two decades, polypropylene (PP) foams have been investigated with the aim of ferroelectret applications, and some products are already on the market. PP-foam ferroelectrets may exhibit piezoelectric d33 coefficients of 600 pC/N and more. Their operating temperature can, however, not be much higher than 60 °C. Recently developed polyethylene-terephthalate (PET) and cyclo-olefin copolymer (COC) foam ferroelectrets show slightly better d33 thermal stabilities, but usually at the price of smaller d33 values. Therefore, the main aim of this work is the development of new thermally stable ferroelectrets with appreciable piezoelectricity. Physical foaming is a promising technique for generating polymer foams from solid films without any pollution or impurity. Supercritical carbon dioxide (CO2) or nitrogen (N2) are usually employed as foaming agents due to their good solubility in several polymers. Polyethylene propylene (PEN) is a polyester with slightly better properties than PET. A “voiding + inflation + stretching” process has been specifically developed to prepare PEN foams. Solid PEN films are saturated with supercritical CO2 at high pressure and then thermally voided at high temperatures. Controlled inflation (Gas-Diffusion Expansion or GDE) is applied in order to adjust the void dimensions. Additional biaxial stretching decreases the void heights, since it is known lens-shaped voids lead to lower elastic moduli and therefore also to stronger piezoelectricity. Both, contact and corona charging are suitable for the electric charging of PEN foams. The light emission from the dielectric-barrier discharges (DBDs) can be clearly observed. Corona charging in a gas of high dielectric strength such as sulfur hexafluoride (SF6) results in higher gas-breakdown strength in the voids and therefore increases the piezoelectricity. PEN foams can exhibit piezoelectric d33 coefficients as high as 500 pC/N. Dielectric-resonance spectra show elastic moduli c33 of 1 − 12 MPa, anti-resonance frequencies of 0.2 − 0.8 MHz, and electromechanical coupling factors of 0.016 − 0.069. As expected, it is found that PEN foams show better thermal stability than PP and PET. Samples charged at room temperature can be utilized up to 80 − 100 °C. Annealing after charging or charging at elevated temperatures may improve thermal stabilities. Samples charged at suitable elevated temperatures show working temperatures as high as 110 − 120 °C. Acoustic measurements at frequencies of 2 Hz − 20 kHz show that PEN foams can be well applied in this frequency range. Fluorinated ethylene-propylene (FEP) copolymers are fluoropolymers with very good physical, chemical and electrical properties. The charge-storage ability of solid FEP films can be significantly improved by adding boron nitride (BN) filler particles. FEP foams are prepared by means of a one-step procedure consisting of CO2 saturation and subsequent in-situ high-temperature voiding. Piezoelectric d33 coefficients up to 40 pC/N are measured on such FEP foams. Mechanical fatigue tests show that the as-prepared PEN and FEP foams are mechanically stable for long periods of time. Although polymer-foam ferroelectrets have a high application potential, their piezoelectric properties strongly depend on the cellular morphology, i.e. on size, shape, and distribution of the voids. On the other hand, controlled preparation of optimized cellular structures is still a technical challenge. Consequently, new ferroelectrets based on polymer-layer system (sandwiches) have been prepared from FEP. By sandwiching an FEP mesh between two solid FEP films and fusing the polymer system with a laser beam, a well-designed uniform macroscopic cellular structure can be formed. Dielectric resonance spectroscopy reveals piezoelectric d33 coefficients as high as 350 pC/N, elastic moduli of about 0.3 MPa, anti-resonance frequencies of about 30 kHz, and electromechanical coupling factors of about 0.05. Samples charged at elevated temperatures show better thermal stabilities than those charged at room temperature, and the higher the charging temperature, the better is the stability. After proper charging at 140 °C, the working temperatures can be as high as 110 − 120 °C. Acoustic measurements at frequencies of 200 Hz − 20 kHz indicate that the FEP layer systems are suitable for applications at least in this range.
Als Schnittstelle zwischen der Lokal- und der Staatsebene konnten die Landkreise ihre Stellung im politischen System Deutschlands bewahren und ausbauen. Optimierungsbedarf hat sich aufgrund des sozioökonomischen, technischen und demographischen Wandel sowie der öffentlichen Finanzkrise ergeben. Kreisgebietsreformmodelle und die Ausweitung der Aufgabenkooperation dominieren die Reformdebatte. Neben den verfassungsrechtlichen Anforderungen und der Akzeptanz der Reform bei den Betroffenen ist der Reformerfolg wesentlich von der Qualität der Umsetzungsstrategie abhängig. Der aktivierenden Einbeziehung der Mitarbeiter in den Reformprozess kommt dabei eine besondere Bedeutung zu.
Untersuchungen PEG-basierter thermo-responsiver Polymeroberflächen zur Steuerung der Zelladhäsion
(2010)
Moderne Methoden für die Einzelzellanalyse werden dank der fortschreitenden Weiterentwicklung immer sensitiver. Dabei steigen jedoch auch die Anforderungen an das Probenmaterial. Viele Aufbereitungsprotokolle adhärenter Zellen beinhalten eine enzymatische Spaltung der Oberflächenproteine, um die Ablösung vom Zellkultursubstrat zu ermöglichen. Verschiedene Methoden, wie die Patch-Clamp-Technik oder eine auf der Markierung extrazellulärer Domänen von Membranproteinen basierende Durchflusszytometrie können dann nur noch eingeschränkt eingesetzt werden. Daher ist die Etablierung neuer Zellablösemethoden dringend notwendig. In der vorliegenden Arbeit werden erstmals PEG-basierte thermo-responsive Oberflächen erfolgreich für die Zellkultur eingesetzt. Dabei wird das zerstörungsfreie Ablösen verschiedener Zelllinien von den Oberflächen durch Temperatursenkung realisiert. Die Funktionalität der Oberflächen wird durch Variation der Polymerstruktur, sowie der Konzentration der Beschichtungslösung, durch Beschichtung der Oberflächen mit einem zelladhäsionsfördernden Protein (Fibronektin) und durch Adsorption zelladhäsionsvermittelnder Peptide (RGD) optimiert. Um den Zellablösungsprozess detaillierter zu untersuchen, wird hier zum ersten Mal der direkte Zellkontakt mit thermo-responsiven Oberflächen mittels oberflächensensitiver Mikroskopie (TIRAF) sichtbar gemacht. Mit dieser Technik sind die exakte Quantifizierung und die Analyse der Reduktion der Zelladhäsionsfläche während des Abkühlens möglich. Hierbei werden in Abhängigkeit von der Zelllinie Unterschiede im Zellverhalten während des Ablösens festgestellt: Zellen, wie eine Brustkrebszelllinie und eine Ovarzelllinie, die bekanntermaßen stärker mit ihrer Umgebung in Kontakt treten, vergrößern im Verlauf des Beobachtungszeitraumes den Abstand zwischen Zellmembran und Oberfläche, reduzieren jedoch ihre Zell-Substratkontaktfläche kaum. Mausfibroblasten hingegen verkleinern drastisch die Zelladhäsionsfläche. Der Ablösungsprozess wird vermutlich aktiv von den Zellen gesteuert. Diese Annahme wird durch zwei Beobachtungen gestützt: Erstens verläuft die Reduktion der Zelladhäsionsfläche bei Einschränkung des Zellmetabolismus durch eine Temperatursenkung auf 4 °C verzögert. Zweitens hinterlassen die Zellen Spuren, die nach dem Ablösen der Zellen auf den Oberflächen zurückbleiben. Mittels Kombination von TIRAF- und TIRF-Mikroskopie werden die Zelladhäsionsfläche und die Aktinstruktur gleichzeitig beobachtet. Die Verknüpfung beider Methoden stellt eine neue Möglichkeit dar, intrazelluläre Prozesse mit der Zellablösung von thermo-responsiven Oberflächen zu korrelieren.
Pektatlyase (Pel-15) aus dem alkalophilen Bodenbakterium Bacillus spec. KSM-P15 ist mit 197 Aminosäuren eines der kleinsten, bekannten β-3-Solenoidproteine. Sie spaltet Polygalakturonsäurederivate in einem Ca2+-abhängigen β-Eliminierungsprozess. Wie bei allen Proteinen dieser Enzymfamilie ist auch die Polypeptidkette von Pel-15 zu einer einsträngigen, rechtsgängigen, parallelen β-Helix aufgewunden. In diesem Strukturmotiv enthält jede Windung drei β-Stränge, die jeweils durch flexible Schleifenbereiche miteinander verbunden sind. Insgesamt acht Windungen stapeln sich in Pel-15 übereinander und bilden entlang der Helixachse flächige, parallele β-Faltblätter aus. Im Bereich dieser β-Faltblätter existiert ein ausgedehntes Netzwerk von Wasserstoffbrückenbindungen, durch das der hydrophobe Kern, der sich im Inneren der β-Helix befindet, vom umgebenden Lösungsmittel abgeschirmt wird. Besondere Abschlussstrukturen an beiden Enden der β-Helix, wie sie typischerweise bei anderen Ver-tretern dieser Strukturklasse ausgeprägt werden, sind in Pel-15 nicht zu beobachten. Stattdessen sind die terminalen Bereiche der β-Helix über Salzbrücken und hydrophobe Seitenkettenkontakte stabilisiert. In der vorliegenden Dissertation wurde die Pektatlyase Pel-15 hinsichtlich ihres Faltungsgleichgewichtes, ihrer enzymatischen Aktivität und der Kinetik ihrer Strukturbildung charakterisiert. In eine evolutionär konservierte Helixwindung wurden destabilisierende Mutationen eingeführt, und deren Auswirkungen mittels spektroskopischer Methoden analysiert. Die Ergebnisse zeigen, dass Pel-15 in Gegenwart des Denaturierungsmittels Guanidiniumhydrochlorid einen hyperfluoreszenten Gleichgewichtsustand (HF) populiert, der nach Messungen von Faltungs- und Entfaltungskinetiken ein konformationelles Ensemble aus den Zuständen HFslow und HFfast darstellt. Diese HF-Zustände sind durch eine hohe Aktivierungsbarriere voneinander getrennt. In Rückfaltungsexperimenten populieren nur etwa 80 % der faltenden Moleküle den Zwischenzustand HFslow, der mit einer Zeitkonstante von ca. 100 s zu HFfast weiterreagiert. Die Denaturierungsmittelabhängigkeit dieser Reaktion ist sehr gering, was eine trans-/cis-Prolylisomerisierung als geschwindigkeitslimitierenden Schritt nahelegt. Die Existenz eines cis-Peptides in der nativen Struktur macht es erforderlich, den denaturierten Zustand als ein Ensemble kinetisch separierter Konformationen, kurz: DSE, zu betrachten, das durch die Spezies Ufast und Uslow populiert wird. Nach dem in dieser Arbeit aufgestellten „Minimalmodell der Pel-15 Faltung“ stehen die HF-Spezies (HFslow, HFfast) mit den Konformationen des DSE in einem thermodynamischen Kreisprozess. Das Modell positioniert HFfast und die native Konformation N auf die „native Seite“ der Aktivierungsbarriere und trägt damit der Tatsache Rechnung, dass die Gleichgewichtseinstellung zwischen diesen Spezies zu schnell ist, um mit manuellen Techniken erfasst zu werden. Die hochaffine Bindung von Ca2+ (Kd = 10 μM) verschiebt sich das Faltungsgleichgewicht bereits in Gegenwart von 1 mM CaCl2 soweit auf die Seite des nativen Zustandes, das HFfast nicht länger nachweisbar ist. Entgegen anfänglicher Vermutungen kommt einer lokalen, evolutionär konservierten Disulfidbrücke im Zentrum der β-Helix eine wichtige Stabilisierungsfunktion zu. Die Disulfidbrücke befindet sich in einem kurzen Schleifenbereich der β-Helix nahe dem aktiven Zentrum. Obwohl ihr Austausch gegen die Reste Val und Ala die freie Stabilisierungsenthalpie des Proteins um ca. 10 kJ/mol reduziert, lässt die Struktur im Bereich der Mutationsstelle keine gravierende Veränderung erkennen. Auch die katalytisch relevante Ca2+-Bindungsaffinität bleibt unbeeinflusst; dennoch zeigen Enzymaktivitätstests für VA-Mutanten eine Reduktion der enzymatischen Aktivität um fast 50 % an. Die evolutionär konservierte Helixwindung im Allgemeinen und die in ihr enthaltene Disulfidbrücke im Besonderen müssen nach den vorliegenden Ergebnissen also eine zentrale Funktion sowohl für die Struktur des katalytischen Zentrums als auch für die Strukturbildung der β-Helix während der Faltungsreaktion besitzen. Die Ergebnisse dieser Arbeit finden in mehreren Punkten Anklang an Faltungseigenschaften, die für andere β -Helixproteine beschrieben wurden. Vor allem aber prädestinieren sie Pel-15 als ein neues, β-helikales Modellprotein. Aufgrund seiner einfachen Topologie, seiner niedrigen Windungszahl und seiner hohen thermodynamischen Stabilität ist Pel-15 sehr gut geeignet, die Determinanten von Stabilität und Strukturbildung des parallelen β-Helix-Motivs in einer Auflösung zu studieren, die aufgrund der Komplexität bestehender β-helikaler Modellsysteme bislang nicht zur Verfügung stand.
The availability of large data sets has allowed researchers to uncover complex properties in complex systems, such as complex networks and human dynamics. A vast number of systems, from the Internet to the brain, power grids, ecosystems, can be represented as large complex networks. Dynamics on and of complex networks has attracted more and more researchers’ interest. In this thesis, first, I introduced a simple but effective dynamical optimization coupling scheme which can realize complete synchronization in networks with undelayed and delayed couplings and enhance the small-world and scale-free networks’ synchronizability. Second, I showed that the robustness of scale-free networks with community structure was enhanced due to the existence of communities in the networks and some of the response patterns were found to coincide with topological communities. My results provide insights into the relationship between network topology and the functional organization in complex networks from another viewpoint. Third, as an important kind of nodes of complex networks, human detailed correspondence dynamics was studied by both data and the model. A new and general type of human correspondence pattern was found and an interacting priority-queues model was introduced to explain it. The model can also embrace a range of realistic social interacting systems such as email and letter communication. My findings provide insight into various human activities both at the individual and network level. Fourth, I present clearly new evidence that human comment behavior in on-line social systems, a different type of interacting human dynamics, is non-Poissonian and a model based on the personal attraction was introduced to explain it. These results are helpful for discovering regular patterns of human behavior in on-line society and the evolution of the public opinion on the virtual as well as real society. Finally, there are conclusion and outlook of human dynamics and complex networks.
With the rise of nanotechnology in the last decade, nanofluidics has been established as a research field and gained increased interest in science and industry. Natural aqueous nanofluidic systems are very complex, there is often a predominance of liquid interfaces or the fluid contains charged or differently shaped colloids. The effects, promoted by these additives, are far from being completely understood and interesting questions arise with regards to the confinement of such complex fluidic systems. A systematic study of nanofluidic processes requires designing suitable experimental model nano – channels with required characteristics. The present work employed thin liquid films (TLFs) as experimental models. They have proven to be useful experimental tools because of their simple geometry, reproducible preparation, and controllable liquid interfaces. The thickness of the channels can be adjusted easily by the concentration of electrolyte in the film forming solution. This way, channel dimensions from 5 – 100 nm are possible, a high flexibility for an experimental system. TLFs have liquid IFs of different charge and properties and they offer the possibility to confine differently shaped ions and molecules to very small spaces, or to subject them to controlled forces. This makes the foam films a unique “device” available to obtain information about fluidic systems in nanometer dimensions. The main goal of this thesis was to study nanofluidic processes using TLFs as models, or tools, and to subtract information about natural systems plus deepen the understanding on physical chemical conditions. The presented work showed that foam films can be used as experimental models to understand the behavior of liquids in nano – sized confinement. In the first part of the thesis, we studied the process of thinning of thin liquid films stabilized with the non – ionic surfactant n – dodecyl – β – maltoside (β – C₁₂G₂) with primary interest in interfacial diffusion processes during the thinning process dependent on surfactant concentration 64. The surfactant concentration in the film forming solutions was varied at constant electrolyte (NaCl) concentration. The velocity of thinning was analyzed combining previously developed theoretical approaches. Qualitative information about the mobility of the surfactant molecules at the film surfaces was obtained. We found that above a certain limiting surfactant concentration the film surfaces were completely immobile and they behaved as non – deformable, which decelerated the thinning process. This follows the predictions for Reynolds flow of liquid between two non – deformable disks. In the second part of the thesis, we designed a TLF nanofluidic system containing rod – like multivalent ions and compared this system to films containing monovalent ions. We presented first results which recognized for the first time the existence of an additional attractive force in the foam films based on the electrostatic interaction between rod – like ions and oppositely charged surfaces. We may speculate that this is an ion bridging component of the disjoining pressure. The results show that for films prepared in presence of spermidine the transformation of the thicker CF to the thinnest NBF is more probable as films prepared with NaCl at similar conditions of electrostatic interaction. This effect is not a result of specific adsorption of any of the ions at the fluid surfaces and it does not lead to any changes in the equilibrium properties of the CF and NBF. Our hypothesis was proven using the trivalent ion Y3+ which does not show ion bridging. The experimental results are compared to theoretical predictions and a quantitative agreement on the system’s energy gain for the change from CF to NBF could be obtained. In the third part of the work, the behavior of nanoparticles in confinement was investigated with respect to their impact on the fluid flow velocity. The particles altered the flow velocity by an unexpected high amount, so that the resulting changes in the dynamic viscosity could not be explained by a realistic change of the fluid viscosity. Only aggregation, flocculation and plug formation can explain the experimental results. The particle systems in the presented thesis had a great impact on the film interfaces due to the stabilizer molecules present in the bulk solution. Finally, the location of the particles with respect to their lateral and vertical arrangement in the film was studied with advanced reflectivity and scattering methods. Neutron Reflectometry studies were performed to investigate the location of nanoparticles in the TLF perpendicular to the IF. For the first time, we study TLFs using grazing incidence small angle X – ray scattering (GISAXS), which is a technique sensitive to the lateral arrangement of particles in confined volumes. This work provides preliminary data on a lateral ordering of particles in the film.
This thesis is concerned with the issue of extinction of populations composed of different types of individuals, and their behavior before extinction and in case of a very late extinction. We approach this question firstly from a strictly probabilistic viewpoint, and secondly from the standpoint of risk analysis related to the extinction of a particular model of population dynamics. In this context we propose several statistical tools. The population size is modeled by a branching process, which is either a continuous-time multitype Bienaymé-Galton-Watson process (BGWc), or its continuous-state counterpart, the multitype Feller diffusion process. We are interested in different kinds of conditioning on non-extinction, and in the associated equilibrium states. These ways of conditioning have been widely studied in the monotype case. However the literature on multitype processes is much less extensive, and there is no systematic work establishing connections between the results for BGWc processes and those for Feller diffusion processes. In the first part of this thesis, we investigate the behavior of the population before its extinction by conditioning the associated branching process X_t on non-extinction (X_t≠0), or more generally on non-extinction in a near future 0≤θ<∞ (X_{t+θ}≠0), and by letting t tend to infinity. We prove the result, new in the multitype framework and for θ>0, that this limit exists and is non-degenerate. This reflects a stationary behavior for the dynamics of the population conditioned on non-extinction, and provides a generalization of the so-called Yaglom limit, corresponding to the case θ=0. In a second step we study the behavior of the population in case of a very late extinction, obtained as the limit when θ tends to infinity of the process conditioned by X_{t+θ}≠0. The resulting conditioned process is a known object in the monotype case (sometimes referred to as Q-process), and has also been studied when X_t is a multitype Feller diffusion process. We investigate the not yet considered case where X_t is a multitype BGWc process and prove the existence of the associated Q-process. In addition, we examine its properties, including the asymptotic ones, and propose several interpretations of the process. Finally, we are interested in interchanging the limits in t and θ, as well as in the not yet studied commutativity of these limits with respect to the high-density-type relationship between BGWc processes and Feller processes. We prove an original and exhaustive list of all possible exchanges of limit (long-time limit in t, increasing delay of extinction θ, diffusion limit). The second part of this work is devoted to the risk analysis related both to the extinction of a population and to its very late extinction. We consider a branching population model (arising notably in the epidemiological context) for which a parameter related to the first moments of the offspring distribution is unknown. We build several estimators adapted to different stages of evolution of the population (phase growth, decay phase, and decay phase when extinction is expected very late), and prove moreover their asymptotic properties (consistency, normality). In particular, we build a least squares estimator adapted to the Q-process, allowing a prediction of the population development in the case of a very late extinction. This would correspond to the best or to the worst-case scenario, depending on whether the population is threatened or invasive. These tools enable us to study the extinction phase of the Bovine Spongiform Encephalopathy epidemic in Great Britain, for which we estimate the infection parameter corresponding to a possible source of horizontal infection persisting after the removal in 1988 of the major route of infection (meat and bone meal). This allows us to predict the evolution of the spread of the disease, including the year of extinction, the number of future cases and the number of infected animals. In particular, we produce a very fine analysis of the evolution of the epidemic in the unlikely event of a very late extinction.
Processing negative imperatives in Bulgarian : evidence from normal, aphasic and child language
(2010)
The incremental nature of sentence processing raises questions about the way the information of incoming functional elements is accessed and subsequently employed in building the syntactic structure which sustains interpretation processes. The present work approaches these questions by investigating the negative particle ne used for sentential negation in Bulgarian and its impact on the overt realisation and the interpretation of imperative inflexion, bound aspectual morphemes and clitic pronouns in child, adult and aphasic language. In contrast to other Slavic languages, Bulgarian negative imperatives (NI) are grammatical only with imperfective verbs. We argue that NI are instantiations of overt aspectual coercion induced by the presence of negation as a temporally sensitive sentential operator. The scope relation between imperative mood, negation, and aspect yields the configuration of the imperfective present which in Bulgarian has to be overtly expressed and prompts the imperfective marking of the predicate. The regular and transparent application of the imperfectivising mechanism relates to the organisation of the TAM categories in Bulgarian which not only promotes the representation of fine perspective shifts but also provides for their distinct morphological expression. Using an elicitation task with NI, we investigated the way 3- and 4-year-old children represent negation in deontic contexts as reflected in their use of aspectually appropriate predicates. Our findings suggest that children are sensitive to the imperfectivity requirement in NI from early on. The imperfectivisation strategies reveal some differences from the target morphological realisation. The relatively low production of target imperfectivised prefixed verbs cannot be explained with morphological processing deficits, but rather indicates that up to the age of five children experience difficulties to apply a progressive view point to accomplishments. Two self-paced reading studies present evidence that neurologically unimpaired Bulgarian speakers profit from the syntactic and prosodic properties of negation during online sentence comprehension. The imperfectivity requirement negation imposes on the predicate speeds up lexical access to imperfective verbs. Similarly, clitic pronouns are more accessible after negation due to the phono-syntactic properties of clitic clusters. As the experimental stimuli do not provide external discourse referents, personal pronouns are parsed as object agreement markers. Without subsequent resolution, personal pronouns appear to be less resource demanding than reflexive clitics. This finding is indicative of the syntax-driven co-reference establishment processes triggered through the lexical specification of reflexive clitics. The results obtained from Bulgarian Broca's aphasics show that they exhibit processing patterns similar to those of the control group. Notwithstanding their slow processing speed, the agrammatic group showed no impairment of negation as reflected by their sensitivity to the aspectual requirements of NI, and to the prosodic constraints on clitic placement. The aphasics were able to parse the structural dependency between mood, negation and aspect as functional categories and to represent it morphologically. The prolonged reaction times (RT) elicited by prefixed verbs indicate increasing processing costs due to the semantic integration of prefixes as perfectivity markers into an overall imperfective construal. This inference is supported by the slower RT to reflexive clitics, which undergo a structurally triggered resolution. Evaluated against cross-linguistic findings, the obtained result strongly suggests that aphasic performance with pronouns depends on the interpretation efforts associated with co-reference establishment and varies due to availability of discourse referents. The investigation of normal and agrammatic processing of Bulgarian NI presents support for the hypothesis that the comprehension deficits in Broca's aphasia result from a slowed-down implementation of syntactic operations. The protracted structure building consumes processing resources and causes temporal mismatches with other processes sustaining sentence comprehension. The investigation of the way Bulgarian children and aphasic speakers process NI reveals that both groups are highly sensitive to the imperfective constraint on the aspectual construal imposed by the presence of negation. The imperfective interpretation requires access to morphologically complex verb forms which contain aspectual morphemes with conflicting semantic information – perfective prefixes and imperfective suffixes. Across modalities, both populations exhibit difficulties in processing prefixed imperfectivised verbs which as predicates of negative imperative sentences reflect the inner perspective the speaker and the addressee need to take towards a potentially bounded situation description.
Production of regular and non-regular verbs : evidence for a lexical entry complexity account
(2010)
The incredible productivity and creativity of language depends on two fundamental resources: a mental lexicon and a mental grammar. Rules of grammar enable us to produce and understand complex phrases we have not encountered before and at the same time constrain the computation of complex expressions. The concepts of the mental lexicon and mental grammar have been thoroughly tested by comparing the use of regular versus non-regular word forms. Regular verbs (e.g. walk-walked) are computed using a suffixation rule in a neural system for grammatical processing; non-regular verbs (run-ran) are retrieved from associative memory. The role of regularity has only been explored for the past tense, where regularity is overtly visible. To explore the representation and encoding of regularity as well as the inflectional processes involved in the production of regular and non-regular verbs, this dissertation investigated three groups of German verbs: regular, irregular and hybrid verbs. Hybrid verbs in German have completely regular conjugation in the present tense and irregular conjugation in the past tense. Articulation latencies were measured while participants named pictures of actions, producing the 3rd person singular of regular, hybrid, and irregular verbs in present and past tense. Studying the production of German verbs in past and present tense, this dissertation explored the complexity of lexical entries as a decisive factor in the production of verbs.
Die Zuwanderung und der Integration von Zuwanderern aus den GUS-Staaten in Deutschland ist eine bedeutsame politische und rechtliche Thematik. Diese Thematik ist in Deutschland bisher noch wenig untersucht und nur in Teilbereichen bearbeitet. Deshalb untersucht das vorgestellte Werk folgende Fragen und Aspekte: Analyse der Zuwanderung aus den GUS-Staaten; Darstellung von Zuwanderungsgruppen aus den GUS-Staaten und ihres rechtlichen Status; die Wellen der Zuwanderung anhand der Zuwanderer aus den GUS-Staaten, einschließlich (Spät)Aussiedlern und jüdische Zuwanderern, tschetschenischen Asylsuchenden, Familienangehörige, Studierende, qualifizierte Arbeitskrafte usw., Analyse der Integrationsprogramme und Integrationsmaßnahmen für die Zuwanderer aus den GUS-Staaten; Darstellung der Integrationschancen und Integrationshemmnisse am Beispiel der Zuwanderer aus den GUS-Staaten, einschließlich das Recht auf Annerkennung der akademischen und beruflichen Qualifikation, das Recht auf Arbeit u.a., die russischen Rückkehr- und (Reintegrations-) Programme für die im Bundesgebiet lebenden Zuwanderer aus den GUS-Staaten – ihre Analyse und Bewertung. Eine weitere Besonderheit der Veröffentlichung besteht darin, dass die Autorin Ihre wissenschaftlichen Ausführungen zur rechtlichen Stellung der GUS-Zuwanderer und zu den Erfolgen bei ihrer Integration, aber auch zu den Integrationshemmnissen und Integrationsproblemen auf eine soziologische Befragung von Zuwanderern aus den GUS-Staaten in den Ländern Brandenburg und Berlin stützt. Die empirische Untersuchung bezieht sich auf den Zeitraum 1991 bis 2009.
Ziel dieser Arbeit ist die Überwindung einer Differenz, die zwischen der Theorie der Phase bzw. der Phasendynamik und ihrer Anwendung in der Zeitreihenanalyse besteht: Während die theoretische Phase eindeutig bestimmt und invariant unter Koordinatentransformationen bzw. gegenüber der jeweils gewählten Observable ist, führen die Standardmethoden zur Abschätzung der Phase aus gegebenen Zeitreihen zu Resultaten, die einerseits von den gewählten Observablen abhängen und so andererseits das jeweilige System keineswegs in eindeutiger und invarianter Weise beschreiben. Um diese Differenz deutlich zu machen, wird die terminologische Unterscheidung von Phase und Protophase eingeführt: Der Terminus Phase wird nur für Variablen verwendet, die dem theoretischen Konzept der Phase entsprechen und daher das jeweilige System in invarianter Weise charakterisieren, während die observablen-abhängigen Abschätzungen der Phase aus Zeitreihen als Protophasen bezeichnet werden. Der zentrale Gegenstand dieser Arbeit ist die Entwicklung einer deterministischen Transformation, die von jeder Protophase eines selbsterhaltenden Oszillators zur eindeutig bestimmten Phase führt. Dies ermöglicht dann die invariante Beschreibung gekoppelter Oszillatoren und ihrer Wechselwirkung. Die Anwendung der Transformation bzw. ihr Effekt wird sowohl an numerischen Beispielen demonstriert - insbesondere wird die Phasentransformation in einem Beispiel auf den Fall von drei gekoppelten Oszillatoren erweitert - als auch an multivariaten Messungen des EKGs, des Pulses und der Atmung, aus denen Phasenmodelle der kardiorespiratorischen Wechselwirkung rekonstruiert werden. Abschließend wird die Phasentransformation für autonome Oszillatoren auf den Fall einer nicht vernachlässigbaren Amplitudenabhängigkeit der Protophase erweitert, was beispielsweise die numerischen Bestimmung der Isochronen des chaotischen Rössler Systems ermöglicht.
In dieser Arbeit wurden die Möglichkeiten und Grenzen für Zirkulardichroismus-Messungen mit Synchrotronstrahlung untersucht. Dazu wurde ein Messaufbau für Zirkulardichroismus-Messungen an zwei Strahlrohren am Berliner Elektronenspeicherring für Synchrotronstrahlung eingesetzt, die für Messungen im Bereich des ultravioletten Lichts geeignet sind. Eigenschaften der Strahlrohre und des Messaufbau wurden in einigen wichtigen Punkten mit kommerziellen Zirkulardichroismus-Spektrometern verglichen. Der Schwerpunkt lag auf der Ausdehnung des zugänglichen Wellenlängenbereichs unterhalb von 180 nm zur Untersuchung des Zirkulardichroismus von Proteinen in diesem Bereich. In diesem Bereich ist es nicht nur die Lichtquelle sondern vor allem die Absorption des Lichts durch Wasser, die den Messbereich bei der Messung biologischer Proben in wässriger Lösung einschränkt. Es wurden Bedingungen gefunden, unter denen der Messbereich auf etwa 160 nm, in einigen Fällen bis auf 130 nm ausgedehnt werden konnte. Dazu musste die Pfadlänge deutlich reduziert werden und verschieden Probenküvetten wurden getestet. Der Einfluss der dabei auftretenden Spannungsdoppelbrechung in den Probenküvetten auf das Messsignal konnte mit einem alternativen Messaufbau deutlich reduziert werden. Systematische Fehler im Messsignal und auftretende Strahlenschäden begrenzen jedoch die Zuverlässigkeit der gemessenen Spektren. Bei Proteinfilmen schränkt die Absorption von Wasser den Messbereich kaum ein. Es wurden jedoch meist deutliche Unterschiede zwischen den Spektren von Proteinfilmen und den Spektren von Proteinen in wässriger Lösung festgestellt. Solange diese Unterschiede nicht minimiert werden können, stellen Proteinfilme keine praktikable Alternative zu Messungen in wässriger Lösung dar.
Nanofibrous mats are interesting scaffold materials for biomedical applications like tissue engineering due to their interconnectivity and their size dimension which mimics the native cell environment. Electrospinning provides a simple route to access such fiber meshes. This thesis addresses the structural and functional control of electrospun fiber mats. In the first section, it is shown that fiber meshes with bimodal size distribution could be obtained in a single-step process by electrospinning. A standard single syringe set-up was used to spin concentrated poly(ε-caprolactone) (PCL) and poly(lactic-co-glycolic acid) (PLGA) solutions in chloroform and meshes with bimodal-sized fiber distribution could be directly obtained by reducing the spinning rate at elevated humidity. Scanning electron microscopy (SEM) and mercury porosity of the meshes suggested a suitable pore size distribution for effective cell infiltration. The bimodal fiber meshes together with unimodal fiber meshes were evaluated for cellular infiltration. While the micrometer fibers in the mixed meshes generate an open pore structure, the submicrometer fibers support cell adhesion and facilitate cell bridging on the large pores. This was revealed by initial cell penetration studies, showing superior ingrowth of epithelial cells into the bimodal meshes compared to a mesh composed of unimodal 1.5 μm fibers. The bimodal fiber meshes together with electrospun nano- and microfiber meshes were further used for the inorganic/organic hybrid fabrication of PCL with calcium carbonate or calcium phosphate, two biorelevant minerals. Such composite structures are attractive for the potential improvement of properties such as stiffness or bioactivity. It was possible to encapsulate nano and mixed sized plasma-treated PCL meshes to areas > 1 mm2 with calcium carbonate using three different mineralization methods including the use of poly(acrylic acid). The additive seemed to be useful in stabilizing amorphous calcium carbonate to effectively fill the space between the electrospun fibers resulting in composite structures. Micro-, nano- and mixed sized fiber meshes were successfully coated within hours by fiber directed crystallization of calcium phosphate using a ten-times concentrated simulated body fluid. It was shown that nanofibers accelerated the calcium phosphate crystallization, as compared to microfibers. In addition, crystallizations performed at static conditions led to hydroxyapatite formations whereas in dynamic conditions brushite coexisted. In the second section, nanofiber functionalization strategies are investigated. First, a one-step process was introduced where a peptide-polymer-conjugate (PLLA-b-CGGRGDS) was co-spun with PLGA in such a way that the peptide is enriched on the surface. It was shown that by adding methanol to the chloroform/blend solution, a dramatic increase of the peptide concentration at the fiber surface could be achieved as determined by X-ray photoelectron spectroscopy (XPS). Peptide accessibility was demonstrated via a contact angle comparison of pure PLGA and RGD-functionalized fiber meshes. In addition, the electrostatic attraction between a RGD-functionalized fiber and a silica bead at pH ~ 4 confirmed the accessibility of the peptide. The bioactivity of these RGD-functionalized fiber meshes was demonstrated using blends containing 18 wt% bioconjugate. These meshes promoted adhesion behavior of fibroblast compared to pure PLGA meshes. In a second functionalization approach, a modular strategy was investigated. In a single step, reactive fiber meshes were fabricated and then functionalized with bioactive molecules. While the electrospinning of the pure reactive polymer poly(pentafluorophenyl methacrylate) (PPFPMA) was feasible, the inherent brittleness of PPFPMA required to spin a PCL blend. Blends and pure PPFPMA showed a two-step functionalization kinetics. An initial fast reaction of the pentafluorophenyl esters with aminoethanol as a model substance was followed by a slow conversion upon further hydrophilization. This was analysed by UV/Vis-spectroscopy of the pentaflurorophenol release upon nucleophilic substitution with the amines. The conversion was confirmed by increased hydrophilicity of the resulting meshes. The PCL/PPFPMA fiber meshes were then used for functionalization with more complex molecules such as saccharides. Aminofunctionalized D-Mannose or D-Galactose was reacted with the active pentafluorophenyl esters as followed by UV/Vis spectroscopy and XPS. The functionality was shown to be bioactive using macrophage cell culture. The meshes functionalized with D-Mannose specifically stimulated the cytokine production of macrophages when lipopolysaccharides were added. This was in contrast to D-Galactose- or aminoethanol-functionalized and unfunctionalized PCL/PPFPMA fiber mats.
Die Ca2+/Calmodulin-aktivierte Serin/Threonin-Phosphatase Calcineurin ist ein Schlüsselmolekül des T-Zell-Rezeptorabhängigen Signalnetzwerkes. Calcineurin aktiviert die Transkriptionsfaktoren der NFATc-Familie durch Dephosphorylierung und reguliert darüber die Expression wichtiger Zytokine und Oberflächenproteine. Die Aktivität von Calcineurin wird durch zahlreiche endogene Proteine moduliert und ist Angriffspunkt der immunsuppressiven Substanzen Cyclosporin A und FK506. In dieser Arbeit wurde der alternative niedermolekulare Calcineurin-NFATc-Inhibitor NCI3 hinsichtlich seiner Effekte auf T-Zell-Rezeptor-abhängige Signalwege charakterisiert. Die Ergebnisse zeigen, daß das Pyrazolopyrimidinderivat NCI3 nichttoxisch und zellmembranpermeabel ist. In T-Zell-Rezeptor-stimulierten primären humanen TH-Zellen unterdrückt NCI3 die Proliferation und IL-2-Produktion (IC50-Wert ~4 µM), da die Dephosphorylierung von NFATc und die anschließende nukleäre Translokation gehemmt wird. NCI3 inhibiert die calcineurinabhängige NFAT- und NF-κB-, aber nicht die AP-1-kontrollierte Reprtergenexpression, in mikromolaren Konzentrationen (IC50-Werte 2 bzw. 7 µM). Im Gegensatz zu Cyclosporin A stört NCI3 nicht die Phosphataseaktivität von Calcineurin, sondern interferiert mit der Calcineurin-NFATc-Bindung. Ein wichtiges endogenes Modulatorprotein für die Calcineurinaktivität ist RCAN1, das vermutlich den Calcineurin-NFATc-Signalweg über einen negativen Rückkopplungsmechanismus reguliert. Hier wurde gezeigt, daß RCAN1 in humanen TH-Zellen exprimiert wird. Die Spleißvariante RCAN1-1 ist in ruhenden T-Zellen basal exprimiert und wird nicht durch T-Zell-Rezeptor-Stimulierung in seiner Expression verändert. RCAN1-4 dagegen ist in ruhenden Zellen kaum zu detektieren und wird stimulierungsabhängig induziert. Durch die Verwendung Calcineurin-NFATc-spezifischer Inhibitoren wie NCI3 wurde gezeigt, daß die RCAN1-4-Induktion durch diesen Signalweg limitiert ist. Die in dieser Arbeit gewonnenen Daten und Erkenntnisse tragen dazu bei, das Verständnis der Funktion und Regulation von Calcineurin in T-Zellen zu vertiefen.
Fire prone Mediterranean-type vegetation systems like those in the Mediterranean Basin and South-Western Australia are global hot spots for plant species diversity. To ensure management programs act to maintain these highly diverse plant communities, it is necessary to get a profound understanding of the crucial mechanisms of coexistence. In the current literature several mechanisms are discussed. The objective of my thesis is to systematically explore the importance of potential mechanisms for maintaining multi-species, fire prone vegetation by modelling. The model I developed is spatially-explicit, stochastic, rule- and individual-based. It is parameterised on data of population dynamics collected over 18 years in the Mediterranean-type shrublands of Eneabba, Western Australia. From 156 woody species of the area seven plant traits have been identified to be relevant for this study: regeneration mode, annual maximum seed production, seed size, maximum crown diameter, drought tolerance, dispersal mode and seed bank type. Trait sets are used for the definition of plant functional types (PFTs). The PFT dynamics are simulated annual by iterating life history processes. In the first part of my thesis I investigate the importance of trade-offs for the maintenance of high diversity in multi-species systems with 288 virtual PFTs. Simulation results show that the trade-off concept can be helpful to identify non-viable combinations of plant traits. However, the Shannon Diversity Index of modelled communities can be high despite of the presence of ‘supertypes’. I conclude, that trade-offs between two traits are less important to explain multi-species coexistence and high diversity than it is predicted by more conceptual models. Several studies show, that seed immigration from the regional seed pool is essential for maintaining local species diversity. However, systematical studies on the seed rain composition to multi-species communities are missing. The results of the simulation experiments, as presented in part two of this thesis, show clearly, that without seed immigration the local species community found in Eneabba drifts towards a state with few coexisting PFTs. With increasing immigration rates the number of simulated coexisting PFTs and Shannon diversity quickly approaches values as also observed in the field. Including the regional seed input in the model is suited to explain more aggregated measures of the local plant community structure such as species richness and diversity. Hence, the seed rain composition should be implemented in future studies. In the third part of my thesis I test the sensitivity of Eneabba PFTs to four different climate change scenarios, considering their impact on both local and regional processes. The results show that climate change clearly has the potential to alter the number of dispersed seeds for most of the Eneabba PFTs and therefore the source of the ‘immigrants’ at the community level. A classification tree analysis shows that, in general, the response to climate change was PFT-specific. In the Eneabba sand plains sensitivity of a PFT to climate change depends on its specific trait combination and on the scenario of environmental change i.e. development of the amount of rainfall and the fire frequency. This result emphasizes that PFT-specific responses and regional process seed immigration should not be ignored in studies dealing with the impact of climate change on future species distribution. The results of the three chapters are finally analysed in a general discussion. The model is discussed and improvements and suggestions are made for future research. My work leads to the following conclusions: i) It is necessary to support modelling with empirical work to explain coexistence in species-rich plant communities. ii) The chosen modelling approach allows considering the complexity of coexistence and improves the understanding of coexistence mechanisms. iii) Field research based assumptions in terms of environmental conditions and plant life histories can relativise the importance of more hypothetic coexistence theories in species-rich systems. In consequence, trade-offs can play a lower role than predicted by conceptual models. iv) Seed immigration is a key process for local coexistence. Its alteration because of climate change should be considered for prognosis of coexistence. Field studies should be carried out to get data on seed rain composition.
We establish elements of a new approach to ellipticity and parametrices within operator algebras on manifolds with higher singularities, only based on some general axiomatic requirements on parameter-dependent operators in suitable scales of spaes. The idea is to model an iterative process with new generations of parameter-dependent operator theories, together with new scales of spaces that satisfy analogous requirements as the original ones, now on a corresponding higher level. The "full" calculus involves two separate theories, one near the tip of the corner and another one at the conical exit to infinity. However, concerning the conical exit to infinity, we establish here a new concrete calculus of edge-degenerate operators which can be iterated to higher singularities.
Die Europäische Währungsunion (EWU) umfasst heute 16 Staaten mit insgesamt 321 Millionen Einwohnern, sie ist mit einem Bruttoinlandsprodukt von 22,9 Billionen Euro einer der größten Wirtschaftsräume der Erde. In den nächsten Jahren wird die EWU durch die Aufnahme der 2004 und 2007 beigetretenen neuen EU-Länder weiter wachsen. Da der Beitritt von der Erfüllung der Kriterien von Maastricht abhängt, erfolgt die Erweiterung im Gegensatz zur 5. Erweiterungsrunde der EU nicht als Block, sondern sequentiell. Nach den Beitritten von Slowenien am 1.1.2007 und der Slowakei zum 1.1.2009 steht der Beitritt eines ersten großen Landes in den nächsten Jahren bevor. Daher stößt die Frage der Effekte eines solchen Beitritts seit geraumer Zeit auf breites Interesse in der ökonomischen Literatur. Das Forschungsziel der Dissertation ist es, die theoretischen Wirkungsmechanismen eines Beitritts der neuen Mitgliedsländer zur Europäischen Währungsunion abzubilden. Hierzu werden mögliche stabilitätspolitische Konsequenzen sowie die Auswirkungen eines Beitritts auf die geografische Wirtschaftsstruktur und das Wachstum dieser Länder in theoretischen Modellen abgeleitet. Die direkten Effekte des Beitritts werden in einem angewandt-theoretischen Modell zudem quantifiziert. Insgesamt wird der Beitritt aus drei verschiedenen Perspektiven analysiert: Erstens werden die Konsequenzen der Währungsunion für die Stabilitätspolitik der neuen Mitgliedsländer im Rahmen eines neukeynesianischen Modells betrachtet. Zweitens werden die mit der Transaktionskostensenkung verbundenen Gewinne in einem angewandten Gleichgewichtsmodell quantifiziert. Drittens werden die wachstumstheoretischen Wirkungen der Finanzmarktintegration in einem dynamischen Gleichgewichtsmodell untersucht. Da die drei Aspekte der makroökonomischen Stabilität, der Transaktionskostensenkung und der dynamischen Wirkungen der Finanzmarktintegration weitgehend unabhängig voneinander auftreten, ist die Verwendung verschiedener Modelle mit geringen Kosten verbunden. In der Gesamtbeurteilung des EWU-Beitritts der neuen EU-Länder kommt diese Arbeit zu einer anderen Einschätzung als bisherige Studien. Die in Teil eins ermittelten stabilitätspolitischen Konsequenzen sind entweder neutral oder implizieren bei Beitritt zur Währungsunion eine größere Stabilität. Die in Teil zwei und drei ermittelten statischen und dynamischen Gewinne eines Beitritts sind zudem erheblich, so dass ein schneller Beitritt zur Währungsunion für die neuen EU-Mitgliedsländer vorteilhaft ist. Unter Berücksichtigung der Ziele der Europäischen Wirtschafts- und Währungsunion (EWWU) müssen hierzu jedoch zwei Bedingungen erfüllt sein. Einerseits sind hinreichend entwickelte Finanzmärkte notwendig, um das Ziel einer Konvergenz der neuen und alten EU-Mitgliedsländer zu erreichen. Andererseits wird der Gesamtraum von einer stärkeren Finanzmarktintegration und einer Senkung der Transaktionskosten profitieren, jedoch durch die Übertragung von Schocks der neuen Mitgliedsländer instabiler. Daher kann der Beitritt der neuen Mitgliedsländer zur EWU für den Gesamtraum negativ sein. Diese Kosten sind nur dann zu rechtfertigen, falls über die schnellere Entwicklung der neuen Mitgliedsstaaten eine höhere Stabilität des Währungsraumes erzielt wird. Das neukeynesianische Wachstumsmodell gibt Hinweise, dass eine solche Entwicklung eintreten könnte.
Am 22. Oktober 1565 beauftragte der Herzog Julius von Braunschweig-Wolfenbüttel seinen Prediger Martin Chemnitz, das literarische Oeuvre des Magisters Cyriacus Spangenberg auf dem Buchmarkt ausfindig zu machen, prunkvoll binden zu lassen und in den herzöglichen Bibliotheksbestand aufzunehmen. 64 Werke mit gut 6000 Seiten hatte der Mansfelder Generaldekan Spangenberg zu diesem Zeitpunkt bereits verfasst, seine Amtskollegen in der sächsischen Grafschaft hatten ihrerseits 64 Bücher veröffentlicht. Bis zum Abgang Spangenbergs aus Mansfeld 1574 verdoppelte sich die Anzahl geistlicher Veröffentlichungen Mansfelder Provenienz. Obwohl zu Lebzeiten breit rezipiert, hat die Publizistik der geistlichen "Druckmetropole" Mansfeld in der Geschichte und Kirchengeschichte wenig Beachtung gefunden. Die vorliegende Dissertation will diese Forschungslücke schließen. Die Mansfelder Prediger verfassten Lehrpredigten, Festpredigten, Trostpredigten, Katechismen, theologische Disputationen, historische Abhandlungen und geistliche Spiele in hoher Zahl und publizierten diese unter geschickter Ausnutzung der Mechanismen der frühneuzeitlichen Buchmarktes reichsweit. Ihre Veröffentlichungen richteten sich an Theologen, "Weltkinder" und "Einfältige". Sie generierten Verbindungen zu den Kirchen und Potentaten Nord- und Süddeutschlands, Frankreichs und der Niederlande und führten zu Kontroversen mit den großen Bildungszentren Mitteldeutschlands Wittenberg, Leipzig und Jena und deren Landesherren. Die Frage nach der Motivation für das Engagement der Mansfelder Prediger auf dem Buchmarkt steht im Zentrum der Untersuchung, die in einem synoptischen Verfahren den Wunsch nach Teilhaberschaft an der Ausbildung der kirchlichen, herrschaftlichen, sozialen und kommunikativen Strukturen als zentrales Motiv der schreibenden Theologen herausarbeitet, aber auch die Absicht der Autoren beweist, der Grafschaft Mansfeld über das Medium Buch als lutherischem Bildungszentrum in Europa Geltung zu verschaffen.
In 1915, Alfred Wegener published his hypotheses of plate tectonics that revolutionised the world for geologists. Since then, many scientists have studied the evolution of continents and especially the geologic structure of orogens: the most visible consequence of tectonic processes. Although the morphology and landscape evolution of mountain belts can be observed due to surface processes, the driving force and dynamics at lithosphere scale are less well understood despite the fact that rocks from deeper levels of orogenic belts are in places exposed at the surface. In this thesis, such formerly deeply-buried (ultra-) high-pressure rocks, in particular eclogite facies series, have been studied in order to reveal details about the formation and exhumation conditions and rates and thus provide insights into the geodynamics of the most spectacular orogenic belt in the world: the Himalaya. The specific area investigated was the Kaghan Valley in Pakistan (NW Himalaya). Following closure of the Tethyan Ocean by ca. 55-50 Ma, the northward subduction of the leading edge of India beneath the Eurasian Plate and subsequent collision initiated a long-lived process of intracrustal thrusting that continues today. The continental crust of India – granitic basement, Paleozoic and Mesozoic cover series and Permo-Triassic dykes, sills and lavas – has been buried partly to mantle depths. Today, these rocks crop out as eclogites, amphibolites and gneisses within the Higher Himalayan Crystalline between low-grade metamorphosed rocks (600-640°C/ ca. 5 kbar) of the Lesser Himalaya and Tethyan sediments. Beside tectonically driven exhumation mechanisms the channel flow model, that describes a denudation focused ductile extrusion of low viscosity material developed in the middle to lower crust beneath the Tibetan Plateau, has been postulated. To get insights into the lithospheric and crustal processes that have initiated and driven the exhumation of this (ultra-) high-pressure rocks, mineralogical, petrological and isotope-geochemical investigations have been performed. They provide insights into 1) the depths and temperatures to which these rocks were buried, 2) the pressures and temperatures the rocks have experienced during their exhumation, 3) the timing of these processes 4) and the velocity with which these rocks have been brought back to the surface. In detail, through microscopical studies, the identification of key minerals, microprobe analyses, standard geothermobarometry and modelling using an effective bulk rock composition it has been shown that published exhumation paths are incomplete. In particular, the eclogites of the northern Kaghan Valley were buried to depths of 140-100 km (36-30 kbar) at 790-640°C. Subsequently, cooling during decompression (exhumation) towards 40-35 km (17-10 kbar) and 630-580°C has been superseded by a phase of reheating to about 720-650°C at roughly the same depth before final exhumation has taken place. In the southern-most part of the study area, amphibolite facies assemblages with formation conditions similar to the deduced reheating phase indicate a juxtaposition of both areas after the eclogite facies stage and thus a stacking of Indian Plate units. Radiometric dating of zircon, titanite and rutile by U-Pb and amphibole and micas by Ar-Ar reveal peak pressure conditions at 47-48 Ma. With a maximum exhumation rate of 14 cm/a these rocks reached the crust-mantle boundary at 40-35 km within 1 Ma. Subsequent exhumation (46-41 Ma, 40-35 km) decelerated to ca. 1 mm/a at the base of the continental crust but rose again to about 2 mm/a in the period of 41-31 Ma, equivalent to 35-20 km. Apatite fission track (AFT) and (U-Th)/He ages from eclogites, amphibolites, micaschists and gneisses yielded moderate Oligocene to Miocene cooling rates of about 10°C/Ma in the high altitude northern parts of the Kaghan Valley using the mineral-pair method. AFT ages are of 24.5±3.8 to 15.6±2.1 Ma whereas apatite (U-Th)/He analyses yielded ages between 21.0±0.6 and 5.3±0.2 Ma. The southern-most part of the Valley is dominated by younger late Miocene to Pliocene apatite fission track ages of 7.6±2.1 and 4.0±0.5 Ma that support earlier tectonically and petrologically findings of a juxtaposition and stack of Indian Plate units. As this nappe is tectonically lowermost, a later distinct exhumation and uplift driven by thrusting along the Main Boundary Thrust is inferred. A multi-stage exhumation path is evident from petrological, isotope-geochemical and low temperature thermochronology investigations. Buoyancy driven exhumation caused an initial rapid exhumation: exhumation as fast as recent normal plate movements (ca. 10 cm/a). As the exhuming units reached the crust-mantle boundary the process slowed down due to changes in buoyancy. Most likely, this exhumation pause has initiated the reheating event that is petrologically evident (e.g. glaucophane rimmed by hornblende, ilmenite overgrowth of rutile). Late stage processes involved widespread thrusting and folding with accompanied regional greenschist facies metamorphism, whereby contemporaneous thrusting on the Batal Thrust (seen by some authors equivalent to the MCT) and back sliding of the Kohistan Arc along the inverse reactivated Main Mantle Thrust caused final exposure of these rocks. Similar circumstances have been seen at Tso Morari, Ladakh, India, 200 km further east where comparable rock assemblages occur. In conclusion, as exhumation was already done well before the initiation of the monsoonal system, climate dependent effects (erosion) appear negligible in comparison to far-field tectonic effects.
Lake ecosystems across the globe have responded to climate warming of recent decades. However, correctly attributing observed changes to altered climatic conditions is complicated by multiple anthropogenic influences on lakes. This thesis contributes to a better understanding of climate impacts on freshwater phytoplankton, which forms the basis of the food chain and decisively influences water quality. The analyses were, for the most part, based on a long-term data set of physical, chemical and biological variables of a shallow, polymictic lake in north-eastern Germany (Müggelsee), which was subject to a simultaneous change in climate and trophic state during the past three decades. Data analysis included constructing a dynamic simulation model, implementing a genetic algorithm to parameterize models, and applying statistical techniques of classification tree and time-series analysis. Model results indicated that climatic factors and trophic state interactively determine the timing of the phytoplankton spring bloom (phenology) in shallow lakes. Under equally mild spring conditions, the phytoplankton spring bloom collapsed earlier under high than under low nutrient availability, due to a switch from a bottom-up driven to a top-down driven collapse. A novel approach to model phenology proved useful to assess the timings of population peaks in an artificially forced zooplankton-phytoplankton system. Mimicking climate warming by lengthening the growing period advanced algal blooms and consequently also peaks in zooplankton abundance. Investigating the reasons for the contrasting development of cyanobacteria during two recent summer heat wave events revealed that anomalously hot weather did not always, as often hypothesized, promote cyanobacteria in the nutrient-rich lake studied. The seasonal timing and duration of heat waves determined whether critical thresholds of thermal stratification, decisive for cyanobacterial bloom formation, were crossed. In addition, the temporal patterns of heat wave events influenced the summer abundance of some zooplankton species, which as predators may serve as a buffer by suppressing phytoplankton bloom formation. This thesis adds to the growing body of evidence that lake ecosystems have strongly responded to climatic changes of recent decades. It reaches beyond many previous studies of climate impacts on lakes by focusing on underlying mechanisms and explicitly considering multiple environmental changes. Key findings show that climate impacts are more severe in nutrient-rich than in nutrient-poor lakes. Hence, to develop lake management plans for the future, limnologists need to seek a comprehensive, mechanistic understanding of overlapping effects of the multi-faceted human footprint on aquatic ecosystems.
Ghana ist ein Musterbeispiel dafür, dass ein Entwicklungsland den Weg zu Good Governance schaffen kann. In vielen Studien wird dem Land im afrikanischen Vergleich heute bescheinigt, hier ein Vorreiter zu sein. Dies ist Ausgangslage der vorliegenden Studie, die der Frage nachgeht „Welche Gründe, Muster und Bedingungen führen zur Entstehung von Good Governance?“. Im Zentrum der vorliegenden Studie steht, wie aus der erkenntnisleitenden Fragestellung hervorgeht, eine empirische Untersuchung zur Entstehung von Good Governance und damit ein Transformationsprozess. Dieser wird bewusst über einen sehr langen Zeitraum (über ein halbes Jahrhundert) untersucht, um auch langfristige Entwicklungen einbeziehen zu können. Die Studie wird mit Hilfe eines „Mixed-Methods-Ansatzes“ sowohl unter Rückgriff auf quantitative als auch auf qualitative Methoden durchgeführt, was sich im Rückblick als sehr ertragreich erwiesen hat. Zunächst wird die Qualität der Governance über den gesamten Zeitraum anhand von sechs Indikatoren gemessen. Danach werden qualitativ die Gründe für die Fort- und Rückschritte analysiert. Dabei lassen sich immer wieder Systematiken herausarbeiten, wie zum Beispiel zirkuläre Entwicklungen, die über viele Jahre den Weg hin zu Good Governance verhinderten, bis jeweils Ausbrüche aus den Kreisläufen geschafft werden konnten. Sowohl in der demokratischen und rechtsstaatlichen Entwicklung als auch bezogen auf die Versorgung der Bevölkerung mit öffentlichen Gütern und die wirtschaftliche Entwicklung. Auch wenn die verschiedenen Bereiche von Good Governance zunächst einzeln untersucht werden, so zeigen sich gleichzeitig deutlich die Wechselwirkungen der Komponenten. Zum Beispiel kristallisiert sich klar heraus, dass Rechtsstaatlichkeit sowohl auf die Stabilität politischer Systeme wirkt, als auch auf die wirtschaftliche Entwicklung. Ebenso beeinflussen diese wiederum die Korruption. Ähnliche Verknüpfungen lassen sich auch bei allen anderen Bereichen nachvollziehen. Die Entwicklung eines Landes kann also nur unter Berücksichtigung eines komplexen Governance-Systems verstanden und erklärt werden. Dabei können die Wechselwirkungen entweder konstruktiv oder destruktiv sein. Die Verflechtungen der einzelnen Bereiche werden in einem Negativ- und dann in einem Positiv-Szenario festgehalten. Diese Idealtypen-Bildung spitzt die Erkenntnisse der vorliegenden Arbeit zu und dient dem analytischen Verständnis der untersuchten Prozesse. Die Untersuchung zeigt, wie Good Governance über das Zusammenspiel verschiedener Faktoren entstehen kann und dass es wissenschaftlich sehr ertragreich ist, Transformationsforschung auf ein komplexes Governance-System auszuweiten. Hierbei werden die vielen empirisch erarbeiteten Ergebnisse zu den einzelnen Transformationen zu komplexen, in sich greifenden Gesamtszenarien zusammengeführt. Da es bisher keine explizite Good Governance-Transformationsforschung gab, wurde hiermit ein erster Schritt in diese Richtung getan. Es wird darüber hinaus deutlich, dass eine Transformation zu Good Governance nicht durch eine kurzfristige Veränderung der Rahmenbedingungen zu erreichen ist. Es geht um kulturelle Veränderungen, um Lernprozesse, um langfristige Entwicklungen, die in der Studie am Beispiel Ghana analysiert werden. In vielen vorangegangenen Transformationsstudien wurde diese zeitliche Komponente vernachlässigt. Ghana hat bereits viele Schritte getan, um einen Weg in die Zukunft und zu Good Governance zu finden. Die Untersuchung dieser Schritte ist Kern der vorliegenden Arbeit. Der Weg Ghanas ist jedoch noch nicht abgeschlossen.
This thesis is concerned with the development of numerical methods using finite difference techniques for the discretization of initial value problems (IVPs) and initial boundary value problems (IBVPs) of certain hyperbolic systems which are first order in time and second order in space. This type of system appears in some formulations of Einstein equations, such as ADM, BSSN, NOR, and the generalized harmonic formulation. For IVP, the stability method proposed in [14] is extended from second and fourth order centered schemes, to 2n-order accuracy, including also the case when some first order derivatives are approximated with off-centered finite difference operators (FDO) and dissipation is added to the right-hand sides of the equations. For the model problem of the wave equation, special attention is paid to the analysis of Courant limits and numerical speeds. Although off-centered FDOs have larger truncation errors than centered FDOs, it is shown that in certain situations, off-centering by just one point can be beneficial for the overall accuracy of the numerical scheme. The wave equation is also analyzed in respect to its initial boundary value problem. All three types of boundaries - outflow, inflow and completely inflow that can appear in this case, are investigated. Using the ghost-point method, 2n-accurate (n = 1, 4) numerical prescriptions are prescribed for each type of boundary. The inflow boundary is also approached using the SAT-SBP method. In the end of the thesis, a 1-D variant of BSSN formulation is derived and some of its IBVPs are considered. The boundary procedures, based on the ghost-point method, are intended to preserve the interior 2n-accuracy. Numerical tests show that this is the case if sufficient dissipation is added to the rhs of the equations.
The origin and evolution of granites has been widely studied because granitoid rocks constitute a major portion of the Earth ́s crust. The formation of granitic magma is, besides temperature mainly triggered by the water content of these rocks. The presence of water in magmas plays an important role due to the ability of aqueous fluids to change the chemical composition of the magma. The exsolution of aqueous fluids from melts is closely linked to a fractionation of elements between the two phases. Then, aqueous fluids migrate to shallower parts of the Earth ́s crust because of it ́s lower density compared to that of melts and adjacent rocks. This process separates fluids and melts, and furthermore, during the ascent, aqueous fluids can react with the adjacent rocks and alter their chemical signature. This is particularly impor- tant during the formation of magmatic-hydrothermal ore deposits or in the late stages of the evolution of magmatic complexes. For a deeper insight to these processes, it is essential to improve our knowledge on element behavior in such systems. In particular, trace elements are used for these studies and petrogenetic interpretations because, unlike major elements, they are not essential for the stability of the phases involved and often reflect magmatic processes with less ambiguity. However, for the majority of important trace elements, the dependence of the geochemical behavior on temperature, pressure, and in particular on the composition of the system are only incompletely or not at all experimentally studied. Former studies often fo- cus on the determination of fluid−melt partition coefficients (Df/m=cfluid/cmelt) of economically interesting elements, e.g., Mo, Sn, Cu, and there are some partitioning data available for ele- ments that are also commonly used for petrological interpretations. At present, no systematic experimental data on trace element behavior in fluid−melt systems as function of pressure, temperature, and chemical composition are available. Additionally, almost all existing data are based on the analysis of quenched phases. This results in substantial uncertainties, particularly for the quenched aqueous fluid because trace element concentrations may change upon cooling. The objective of this PhD thesis consisted in the study of fluid−melt partition coefficients between aqueous solutions and granitic melts for different trace elements (Rb, Sr, Ba, La, Y, and Yb) as a function of temperature, pressure, salinity of the fluid, composition of the melt, and experimental and analytical approach. The latter included the refinement of an existing method to measure trace element concentrations in fluids equilibrated with silicate melts di- rectly at elevated pressures and temperatures using a hydrothermal diamond-anvil cell and synchrotron radiation X-ray fluorescence microanalysis. The application of this in-situ method enables to avoid the main source of error in data from quench experiments, i.e., trace element concentration in the fluid. A comparison of the in-situ results to data of conventional quench experiments allows a critical evaluation of quench data from this study and literature data. In detail, starting materials consisted of a suite of trace element doped haplogranitic glasses with ASI varying between 0.8 and 1.4 and H2O or a chloridic solution with m NaCl/KCl=1 and different salinities (1.16 to 3.56 m (NaCl+KCl)). Experiments were performed at 750 to 950◦C and 0.2 or 0.5 GPa using conventional quench devices (externally and internally heated pressure vessels) with different quench rates, and at 750◦C and 0.2 to 1.4 GPa with in-situ analysis of the trace element concentration in the fluids. The fluid−melt partitioning data of all studied trace elements show 1. a preference for the melt (Df/m < 1) at all studied conditions, 2. one to two orders of magnitude higher Df/m using chloridic solutions compared to experiments with H2O, 3. a clear dependence on the melt composition for fluid−melt partitioning of Sr, Ba, La, Y, and Yb in experiments using chloridic solutions, 4. quench rate−related differences of fluid−melt partition coefficients of Rb and Sr, and 5. distinctly higher fluid−melt partitioning data obtained from in-situ experiments than from comparable quench runs, particularly in the case of H2O as starting solution. The data point to a preference of all studied trace elements for the melt even at fairly high salinities, which contrasts with other experimental studies, but is supported by data from studies of natural co-genetically trapped fluid and melt inclusions. The in-situ measurements of trace element concentrations in the fluid verify that aqueous fluids will change their composition upon cooling, which is in particular important for Cl free systems. The distinct differences of the in-situ results to quench data of this study as well as to data from the literature signify the im- portance of a careful fluid sampling and analysis. Therefore, the direct measurement of trace element contents in fluids equilibrated with silicate melts at elevated PT conditions represents an important development to obtain more reliable fluid−melt partition coefficients. For further improvement, both the aqueous fluid and the silicate melt need to be analyzed in-situ because partitioning data that are based on the direct measurement of the trace element content in the fluid and analysis of a quenched melt are still not completely free of quench effects. At present, all available data on element complexation in aqueous fluids in equilibrium with silicate melts at high PT are indirectly derived from partitioning data, which involves in these experiments assumptions on the species present in the fluid. However, the activities of chemical components in these partitioning experiments are not well constrained, which is required for the definition of exchange equilibria between melt and fluid species. For example, the melt-dependent variation of partition coefficient observed for Sr imply that this element can not only be complexed by Cl− as suggested previously. The data indicate a more complicated complexation of Sr in the aqueous fluid. To verify this hypothesis, the in-situ setup was also used to determine strontium complexation in fluids equilibrated with silicate melts at desired PT conditions by the application of X-ray absorption near edge structure (XANES) spectroscopy. First results show a strong effect of both fluid and melt composition on the resulting XANES spectra, which indicates different complexation environments for Sr.
Calibration of the global hydrological model WGHM with water mass variations from GRACE gravity data
(2010)
Since the start-up of the GRACE (Gravity Recovery And Climate Experiment) mission in 2002 time dependent global maps of the Earth's gravity field are available to study geophysical and climatologically-driven mass redistributions on the Earth's surface. In particular, GRACE observations of total water storage changes (TWSV) provide a comprehensive data set for analysing the water cycle on large scales. Therefore they are invaluable for validation and calibration of large-scale hydrological models as the WaterGAP Global Hydrology Model (WGHM) which simulates the continental water cycle including its most important components, such as soil, snow, canopy, surface- and groundwater. Hitherto, WGHM exhibits significant differences to GRACE, especially for the seasonal amplitude of TWSV. The need for a validation of hydrological models is further highlighted by large differences between several global models, e.g. WGHM, the Global Land Data Assimilation System (GLDAS) and the Land Dynamics model (LaD). For this purpose, GRACE links geodetic and hydrological research aspects. This link demands the development of adequate data integration methods on both sides, forming the main objectives of this work. They include the derivation of accurate GRACE-based water storage changes, the development of strategies to integrate GRACE data into a global hydrological model as well as a calibration method, followed by the re-calibration of WGHM in order to analyse process and model responses. To achieve these aims, GRACE filter tools for the derivation of regionally averaged TWSV were evaluated for specific river basins. Here, a decorrelation filter using GRACE orbits for its design is most efficient among the tested methods. Consistency in data and equal spatial resolution between observed and simulated TWSV were realised by the inclusion of all most important hydrological processes and an equal filtering of both data sets. Appropriate calibration parameters were derived by a WGHM sensitivity analysis against TWSV. Finally, a multi-objective calibration framework was developed to constrain model predictions by both river discharge and GRACE TWSV, realised with a respective evolutionary method, the ε-Non-dominated-Sorting-Genetic-Algorithm-II (ε-NSGAII). Model calibration was done for the 28 largest river basins worldwide and for most of them improved simulation results were achieved with regard to both objectives. From the multi-objective approach more reliable and consistent simulations of TWSV within the continental water cycle were gained and possible model structure errors or mis-modelled processes for specific river basins detected. For tropical regions as such, the seasonal amplitude of water mass variations has increased. The findings lead to an improved understanding of hydrological processes and their representation in the global model. Finally, the robustness of the results is analysed with respect to GRACE and runoff measurement errors. As a main conclusion obtained from the results, not only soil water and snow storage but also groundwater and surface water storage have to be included in the comparison of the modelled and GRACE-derived total water budged data. Regarding model calibration, the regional varying distribution of parameter sensitivity suggests to tune only parameter of important processes within each region. Furthermore, observations of single storage components beside runoff are necessary to improve signal amplitudes and timing of simulated TWSV as well as to evaluate them with higher accuracy. The results of this work highlight the valuable nature of GRACE data when merged into large-scale hydrological modelling and depict methods to improve large-scale hydrological models.
Coupling of the electrical, mechanical and optical response in polymer/liquid-crystal composites
(2010)
Micrometer-sized liquid-crystal (LC) droplets embedded in a polymer matrix may enable optical switching in the composite film through the alignment of the LC director along an external electric field. When a ferroelectric material is used as host polymer, the electric field generated by the piezoelectric effect can orient the director of the LC under an applied mechanical stress, making these materials interesting candidates for piezo-optical devices. In this work, polymer-dispersed liquid crystals (PDLCs) are prepared from poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)) and a nematic liquid crystal (LC). The anchoring effect is studied by means of dielectric relaxation spectroscopy. Two dispersion regions are observed in the dielectric spectra of the pure P(VDF-TrFE) film. They are related to the glass transition and to a charge-carrier relaxation, respectively. In PDLC films containing 10 and 60 wt% LC, an additional, bias-field-dependent relaxation peak is found that can be attributed to the motion of LC molecules. Due to the anchoring effect of the LC molecules, this relaxation process is slowed down considerably, when compared with the related process in the pure LC. The electro-optical and piezo-optical behavior of PDLC films containing 10 and 60 wt% LCs is investigated. In addition to the refractive-index mismatch between the polymer matrix and the LC molecules, the interaction between the polymer dipoles and the LC molecules at the droplet interface influences the light-scattering behavior of the PDLC films. For the first time, it was shown that the electric field generated by the application of a mechanical stress may lead to changes in the transmittance of a PDLC film. Such a piezo-optical PDLC material may be useful e.g. in sensing and visualization applications. Compared to a non-polar matrix polymer, the polar matrix polymer exhibits a strong interaction with the LC molecules at the polymer/LC interface which affects the electro-optical effect of the PDLC films and prevents a larger increase in optical transmission.
This thesis presents methods for automated synthesis of flexible chip multiprocessor systems from parallel programs targeted at FPGAs to exploit both task-level parallelism and architecture customization. Automated synthesis is necessitated by the complexity of the design space. A detailed description of the design space is provided in order to determine which parameters should be modeled to facilitate automated synthesis by optimizing a cost function, the emphasis being placed on inclusive modeling of parameters from application, architectural and physical subspaces, as well as their joint coverage in order to avoid pre-constraining the design space. Given a parallel program and a set of an IP library, the automated synthesis problem is to simultaneously (i) select processors (ii) map and schedule tasks to them, and (iii) select one or several networks for inter-task communications such that design constraints and optimization objectives are met. The research objective in this thesis is to find a suitable model for automated synthesis, and to evaluate methods of using the model for architectural optimizations. Our contributions are a holistic approach for the design of such systems, corresponding models to facilitate automated synthesis, evaluation of optimization methods using state of the art integer linear and answer set programming, as well as the development of synthesis heuristics to solve runtime challenges.
Die Analyse vergleicht Installationen von Bruce Nauman und Olafur Eliasson ausgehend von der Fragestellung, wie sich die künstlerischen Performativitätsstrategien der 1960er/70er Jahren und die der zeitgenössischen Kunst in ihren Wirkungen und Effekten unterscheiden lassen. Dabei werden die Positionen der beiden Künstler als paradigmatisch für eine Ästhetik des Performativen angesehen. Neben dem Vergleich der Künstler steht die theoretische Auseinandersetzung mit der Diskursfigur der Performativität sowie deren methodischen Anwendbarkeit in der Kunstwissenschaft im Vordergrund. Während sich Installationen der 1960er/70er Jahre besonders durch die psycho-physische Einwirkung auf die Sinneswahrnehmung des Betrachters auszeichnen und durchaus Schockeffekte beim Betrachter hervorrufen, befasst sich die zeitgenössische Kunstpraxis vornehmlich mit visuellen und poetischen Effekten, die eine kontemplative Rezeptionshaltung des Betrachters einfordern. Bruce Nauman war es ein Anliegen, den tradierten Status des Kunstwerks als ein zu Betrachtendes, das sich durch Begriffe wie Form, Ursprung und Originalität fassen ließ, in Frage zu stellen und stattdessen eine reale leibliche Erfahrung für den Betrachter nachvollziehbar werden zu lassen. Künstlern wie Olafur Eliasson geht es in den künstlerischen Produktionen vor allem um die Wahrnehmung der Wahrnehmung sowie der Erzeugung von Präsenzeffekten. Mit dem Aufkommen solcher Verfahren wurde deutlich, dass performative Installationen nach anderen Beschreibungsformen verlangten und, dass diese durch eine Ästhetik des Performativen gefasst werden können. Wie genau vollzieht sich der Wandel von den performativen Strategien der 1960er/70er Jahre zu denen der zeitgenössischen Installationskünstlern? Verläuft dieser vom Schock zur Poesie?
The genome can be considered the blueprint for an organism. Composed of DNA, it harbours all organism-specific instructions for the synthesis of all structural components and their associated functions. The role of carriers of actual molecular structure and functions was believed to be exclusively assumed by proteins encoded in particular segments of the genome, the genes. In the process of converting the information stored genes into functional proteins, RNA – a third major molecule class – was discovered early on to act a messenger by copying the genomic information and relaying it to the protein-synthesizing machinery. Furthermore, RNA molecules were identified to assist in the assembly of amino acids into native proteins. For a long time, these - rather passive - roles were thought to be the sole purpose of RNA. However, in recent years, new discoveries have led to a radical revision of this view. First, RNA molecules with catalytic functions - thought to be the exclusive domain of proteins - were discovered. Then, scientists realized that much more of the genomic sequence is transcribed into RNA molecules than there are proteins in cells begging the question what the function of all these molecules are. Furthermore, very short and altogether new types of RNA molecules seemingly playing a critical role in orchestrating cellular processes were discovered. Thus, RNA has become a central research topic in molecular biology, even to the extent that some researcher dub cells as “RNA machines”. This thesis aims to contribute towards our understanding of RNA-related phenomena by applying Bioinformatics means. First, we performed a genome-wide screen to identify sites at which the chemical composition of DNA (the genotype) critically influences phenotypic traits (the phenotype) of the model plant Arabidopsis thaliana. Whole genome hybridisation arrays were used and an informatics strategy developed, to identify polymorphic sites from hybridisation to genomic DNA. Following this approach, not only were genotype-phenotype associations discovered across the entire Arabidopsis genome, but also regions not currently known to encode proteins, thus representing candidate sites for novel RNA functional molecules. By statistically associating them with phenotypic traits, clues as to their particular functions were obtained. Furthermore, these candidate regions were subjected to a novel RNA-function classification prediction method developed as part of this thesis. While determining the chemical structure (the sequence) of candidate RNA molecules is relatively straightforward, the elucidation of its structure-function relationship is much more challenging. Towards this end, we devised and implemented a novel algorithmic approach to predict the structural and, thereby, functional class of RNA molecules. In this algorithm, the concept of treating RNA molecule structures as graphs was introduced. We demonstrate that this abstraction of the actual structure leads to meaningful results that may greatly assist in the characterization of novel RNA molecules. Furthermore, by using graph-theoretic properties as descriptors of structure, we indentified particular structural features of RNA molecules that may determine their function, thus providing new insights into the structure-function relationships of RNA. The method (termed Grapple) has been made available to the scientific community as a web-based service. RNA has taken centre stage in molecular biology research and novel discoveries can be expected to further solidify the central role of RNA in the origin and support of life on earth. As illustrated by this thesis, Bioinformatics methods will continue to play an essential role in these discoveries.
CHAMP (CHAllenging Minisatellite Payload) is a German small satellite mission to study the earth's gravity field, magnetic field and upper atmosphere. Thanks to the good condition of the satellite so far, the planned 5 years mission is extended to year 2009. The satellite provides continuously a large quantity of measurement data for the purpose of Earth study. The measurements of the magnetic field are undertaken by two Fluxgate Magnetometers (vector magnetometer) and one Overhauser Magnetometer (scalar magnetometer) flown on CHAMP. In order to ensure the quality of the data during the whole mission, the calibration of the magnetometers has to be performed routinely in orbit. The scalar magnetometer serves as the magnetic reference and its readings are compared with the readings of the vector magnetometer. The readings of the vector magnetometer are corrected by the parameters that are derived from this comparison, which is called the scalar calibration. In the routine processing, these calibration parameters are updated every 15 days by means of scalar calibration. There are also magnetic effects coming from the satellite which disturb the measurements. Most of them have been characterized during tests before launch. Among them are the remanent magnetization of the spacecraft and fields generated by currents. They are all considered to be constant over the mission life. The 8 years of operation experience allow us to investigate the long-term behaviors of the magnetometers and the satellite systems. According to the investigation, it was found that for example the scale factors of the FGM show obvious long-term changes which can be described by logarithmic functions. The other parameters (offsets and angles between the three components) can be considered constant. If these continuous parameters are applied for the FGM data processing, the disagreement between the OVM and the FGM readings is limited to \pm1nT over the whole mission. This demonstrates, the magnetometers on CHAMP exhibit a very good stability. However, the daily correction of the parameter Z component offset of the FGM improves the agreement between the magnetometers markedly. The Z component offset plays a very important role for the data quality. It exhibits a linear relationship with the standard deviation of the disagreement between the OVM and the FGM readings. After Z offset correction, the errors are limited to \pm0.5nT (equivalent to a standard deviation of 0.2nT). We improved the corrections of the spacecraft field which are not taken into account in the routine processing. Such disturbance field, e.g. from the power supply system of the satellite, show some systematic errors in the FGM data and are misinterpreted in 9-parameter calibration, which brings false local time related variation of the calibration parameters. These corrections are made by applying a mathematical model to the measured currents. This non-linear model is derived from an inversion technique. If the disturbance field of the satellite body are fully corrected, the standard deviation of scalar error \triangle B remains about 0.1nT. Additionally, in order to keep the OVM readings a reliable standard, the imperfect coefficients of the torquer current correction for the OVM are redetermined by solving a minimization problem. The temporal variation of the spacecraft remanent field is investigated. It was found that the average magnetic moment of the magneto-torquers reflects well the moment of the satellite. This allows for a continuous correction of the spacecraft field. The reasons for the possible unknown systemic error are discussed in this thesis. Particularly, both temperature uncertainties and time errors have influence on the FGM data. Based on the results of this thesis the data processing of future magnetic missions can be designed in an improved way. In particular, the upcoming ESA mission Swarm can take advantage of our findings and provide all the auxiliary measurements needed for a proper recovery of the ambient magnetic field.