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Ficción herética
(2019)
La metáfora de la «isla» en la narrativa cubana contemporánea engloba toda una serie de complejidades simbólicas dependientes de la vivencia del espacio y el tiempo. Su potencial visual se manifiesta u oculta las propias vivencias insulares de los escritores cubanos. En los últimos 30 años en Cuba, los fenómenos políticos económicos y sociales han modificado categóricamente la percepción y la configuración del plano social e individual frente a las exigencias globales (Fornet 2006, Rojas 1999, 2002, 2006). Se ha confirmado una sensación de acinesia e ingravidez (Casamayor 2013) y se ha presentado una actitud «herética» por parte de los narradores cubanos, quienes se confrontan con las ideas de la postmodernidad, lo postsoviético o postutópico, reafirmando así una sensibilidad presentista (Guerrero 2016). Estos autores presentan resonancias y reivindicaciones de los imaginarios insulares de autores y de tradiciones estéticas dentro y fuera de la isla como José Lezama Lima, Virgilio Piñera, Guillermo Cabrera Infante, Reinaldo Arenas y Severo Sarduy). El análisis de las écfrasis insulares permite examinar las dinámicas de representación y de sentido: disimulación: la disimulación, la anamorfosis y la trompe l’oeil (Sarduy 1981). La novela Tuyo es el reino (1998) de Abilio Estévez es un modelo desde el que se localizará las relaciones de sentido entre canon literario y los referentes socioculturales de las variaciones somatopológicas de la isla en la narrativa cubana actual: Ena Lucía Portela, Atilio Caballero, Antonio José Ponte, Daniel Díaz Mantilla, Emerio Medina, Orlando Luis Pardo, Anisley Negrin y Ahmel Echeverría, entre otros.
Die funktionelle Charakterisierung von therapeutisch relevanten Proteinen kann bereits durch die Bereitstellung des Zielproteins in adäquaten Mengen limitierend sein. Dies trifft besonders auf Membranproteine zu, die aufgrund von zytotoxischen Effekten auf die Produktionszelllinie und der Tendenz Aggregate zu bilden, in niedrigen Ausbeuten an aktivem Protein resultieren können. Der lebende Organismus kann durch die Verwendung von translationsaktiven Zelllysaten umgangen werden- die Grundlage der zellfreien Proteinsynthese. Zu Beginn der Arbeit wurde die ATP-abhängige Translation eines Lysates auf der Basis von kultivierten Insektenzellen (Sf21) analysiert. Für diesen Zweck wurde ein ATP-bindendes Aptamer eingesetzt, durch welches die Translation der Nanoluziferase reguliert werden konnte. Durch die dargestellte Applizierung von Aptameren, könnten diese zukünftig in zellfreien Systemen für die Visualisierung der Transkription und Translation eingesetzt werden, wodurch zum Beispiel komplexe Prozesse validiert werden können.
Neben der reinen Proteinherstellung können Faktoren wie posttranslationale Modifikationen sowie eine Integration in eine lipidische Membran essentiell für die Funktionalität des Membranproteins sein. Im zweiten Abschnitt konnte, im zellfreien Sf21-System, für den G-Protein-gekoppelten Rezeptor Endothelin B sowohl eine Integration in die endogen vorhandenen Endoplasmatisch Retikulum-basierten Membranstrukturen als auch Glykosylierungen, identifiziert werden.
Auf der Grundlage der erfolgreichen Synthese des ET-B-Rezeptors wurden verschiedene Methoden zur Fluoreszenzmarkierung des Adenosin-Rezeptors A2a (Adora2a) angewandt und optimiert. Im dritten Abschnitt wurde der Adora2a mit Hilfe einer vorbeladenen tRNA, welche an eine fluoreszierende Aminosäure gekoppelt war, im zellfreien Chinesischen Zwerghamster Ovarien (CHO)-System markiert. Zusätzlich konnte durch den Einsatz eines modifizierten tRNA/Aminoacyl-tRNA-Synthetase-Paares eine nicht-kanonische Aminosäure an Position eines integrierten Amber-Stopcodon in die Polypeptidkette eingebaut und die funktionelle Gruppe im Anschluss an einen Fluoreszenzfarbstoff gekoppelt werden. Aufgrund des offenen Charakters eignen sich zellfreie Proteinsynthesesysteme besonders für eine Integration von exogenen Komponenten in den Translationsprozess. Mit Hilfe der Fluoreszenzmarkierung wurde eine ligandvermittelte Konformationsänderung im Adora2a über einen Biolumineszenz-Resonanzenergietransfer detektiert. Durch die Etablierung der Amber-Suppression wurde darüber hinaus das Hormon Erythropoetin pegyliert, wodurch Eigenschaften wie Stabilität und Halbwertszeit des Proteins verändert wurden.
Zu guter Letzt wurde ein neues tRNA/Aminoacyl-tRNA-Synthetase-Paar auf Basis der Methanosarcina mazei Pyrrolysin-Synthetase etabliert, um das Repertoire an nicht-kanonischen Aminosäuren und den damit verbundenen Kopplungsreaktionen zu erweitern. Zusammenfassend wurden die Potenziale zellfreier Systeme in Bezug auf der Herstellung von komplexen Membranproteinen und der Charakterisierung dieser durch die Einbringung einer positionsspezifischen Fluoreszenzmarkierung verdeutlicht, wodurch neue Möglichkeiten für die Analyse und Funktionalisierung von komplexen Proteinen geschaffen wurden.
For millennia, humans have affected landscapes all over the world. Due to horizontal expansion, agriculture plays a major role in the process of fragmentation. This process is caused by a substitution of natural habitats by agricultural land leading to agricultural landscapes. These landscapes are characterized by an alternation of agriculture and other land use like forests. In addition, there are landscape elements of natural origin like small water bodies. Areas of different land use are beside each other like patches, or fragments. They are physically distinguishable which makes them look like a patchwork from an aerial perspective. These fragments are each an own ecosystem with conditions and properties that differ from their adjacent fragments. As open systems, they are in exchange of information, matter and energy across their boundaries. These boundary areas are called transition zones. Here, the habitat properties and environmental conditions are altered compared to the interior of the fragments. This changes the abundance and the composition of species in the transition zones, which in turn has a feedback effect on the environmental conditions.
The literature mainly offers information and insights on species abundance and composition in forested transition zones. Abiotic effects, the gradual changes in energy and matter, received less attention. In addition, little is known about non-forested transition zones. For example, the effects on agricultural yield in transition zones of an altered microclimate, matter dynamics or different light regimes are hardly researched or understood. The processes in transition zones are closely connected with altered provisioning and regulating ecosystem services. To disentangle the mechanisms and to upscale the effects, models can be used.
My thesis provides insights into these topics: literature was reviewed and a conceptual framework for the quantitative description of gradients of matter and energy in transition zones was introduced. The results of measurements of environmental gradients like microclimate, aboveground biomass and soil carbon and nitrogen content are presented that span from within the forest into arable land. Both the measurements and the literature review could not validate a transition zone of 100 m for abiotic effects. Although this value is often reported and used in the literature, it is likely to be smaller.
Further, the measurements suggest that on the one hand trees in transition zones are smaller compared to those in the interior of the fragments, while on the other hand less biomass was measured in the arable lands’ transition zone. These results support the hypothesis that less carbon is stored in the aboveground biomass in transition zones. The soil at the edge (zero line) between adjacent forest and arable land contains more nitrogen and carbon content compared to the interior of the fragments. One-year measurements in the transition zone also provided evidence that microclimate is different compared to the fragments’ interior.
To predict the possible yield decreases that transition zones might cause, a modelling approach was developed. Using a small virtual landscape, I modelled the effect of a forest fragment shading the adjacent arable land and the effects of this on yield using the MONICA crop growth model. In the transition zone yield was less compared to the interior due to shading. The results of the simulations were upscaled to the landscape level and exemplarily calculated for the arable land of a whole region in Brandenburg, Germany.
The major findings of my thesis are: (1) Transition zones are likely to be much smaller than assumed in the scientific literature; (2) transition zones aren’t solely a phenomenon of forested ecosystems, but significantly extend into arable land as well; (3) empirical and modelling results show that transition zones encompass biotic and abiotic changes that are likely to be important to a variety of agricultural landscape ecosystem services.
Species assembly from a regional pool into local metacommunities and how they colonize and coexist over time and space is essential to understand how communities response to their environment including abiotic and biotic factors. In highly disturbed landscapes, connectivity of isolated habitat patches is essential to maintain biodiversity and the entire ecosystem functioning. In northeast Germany, a high density of the small water bodies called kettle holes, are good systems to study metacommunities due to their condition as “aquatic islands” suitable for hygrophilous species that are surrounded by in unsuitable matrix of crop fields. The main objective of this thesis was to infer the main ecological processes shaping plant communities and their response to the environment, from biodiversity patterns and key life-history traits involved in connectivity using ecological and genetic approaches; and to provide first insights of the role of kettle holes harboring wild-bee species as important mobile linkers connecting plant communities in this insular system.
t a community level, I compared plant diversity patterns and trait composition in ephemeral vs. permanent kettle holes). My results showed that types of kettle holes act as environmental filers shaping plant diversity, community-composition and trait-distribution, suggesting species sorting and niche processes in both types of kettle holes. At a population level, I further analyzed the role of dispersal and reproductive strategies of four selected species occurring in permanent kettle holes. Using microsatellites, I found that breeding system (degree of clonality), is the main factor shaping genetic diversity and genetic divergence. Although, higher gene flow and lower genetic differentiation among populations in wind vs. insect pollinated species was also found, suggesting that dispersal mechanisms played a role related to gene flow and connectivity. For most flowering plants, pollinators play an important role connecting communities. Therefore, as a first insight of the potential mobile linkers of these plant communities, I investigated the diversity wild-bees occurring in these kettle holes. My main results showed that local habitat quality (flower resources) had a positive effect on bee diversity, while habitat heterogeneity (number of natural landscape elements surrounding kettle holes 100–300m), was negatively correlated.
This thesis covers from genetic flow at individual and population level to plant community assembly. My results showed how patterns of biodiversity, dispersal and reproduction strategies in plant population and communities can be used to infer ecological processes. In addition, I showed the importance of life-history traits and the relationship between species and their abiotic and biotic interactions. Furthermore, I included a different level of mobile linkers (pollinators) for a better understanding of another level of the system. This integration is essential to understand how communities respond to their surrounding environment and how disturbances such as agriculture, land-use and climate change might affect them. I highlight the need to integrate many scientific areas covering from genes to ecosystems at different spatiotemporal scales for a better understanding, management and conservation of our ecosystems.
Aluminum oxide is an Earth-abundant geological material, and its interaction with water is of crucial importance for geochemical and environmental processes. Some aluminum oxide surfaces are also known to be useful in heterogeneous catalysis, while the surface chemistry of aqueous oxide interfaces determines the corrosion, growth and dissolution of such materials. In this doctoral work, we looked mainly at the (0001) surface of α-Al 2 O 3 and its reactivity towards water. In particular, a great focus of this work is dedicated to simulate and address the vibrational spectra of water adsorbed on the α-alumina(0001) surface in various conditions and at different coverages. In fact, the main source of comparison and inspiration for this work comes from the collaboration with the “Interfacial Molecular Spectroscopy” group led by Dr. R. Kramer Campen at the Fritz-Haber Institute of the MPG in Berlin. The expertise of our project partners in surface-sensitive Vibrational Sum Frequency (VSF) generation spectroscopy was crucial to develop and adapt specific simulation schemes used in this work. Methodologically, the main approach employed in this thesis is Ab Initio Molecular Dynamics (AIMD) based on periodic Density Functional Theory (DFT) using the PBE functional with D2 dispersion correction. The analysis of vibrational frequencies from both a static and a dynamic, finite-temperature perspective offers the ability to investigate the water / aluminum oxide interface in close connection to experiment.
The first project presented in this work considers the characterization of dissociatively adsorbed deuterated water on the Al-terminated (0001) surface. This particular structure is known from both experiment and theory to be the thermodynamically most stable surface termination of α-alumina in Ultra-High Vacuum (UHV) conditions. Based on experiments performed by our colleagues at FHI, different adsorption sites and products have been proposed and identified for D 2 O. While previous theoretical investigations only looked at vibrational frequencies of dissociated OD groups by staticNormal Modes Analysis (NMA), we rather employed a more sophisticated approach to directly assess vibrational spectra (like IR and VSF) at finite temperature from AIMD. In this work, we have employed a recent implementation which makes use of velocity-velocity autocorrelation functions to simulate such spectral responses of O-H(D) bonds. This approach allows for an efficient and qualitatively accurate estimation of Vibrational Densities of States (VDOS) as well as IR and VSF spectra, which are then tested against experimental spectra from our collaborators.
In order to extend previous work on unimolecularly dissociated water on α-Al 2 O 3 , we then considered a different system, namely, a fully hydroxylated (0001) surface, which results from the reconstruction of the UHV-stable Al-terminated surface at high water contents. This model is then further extended by considering a hydroxylated surface with additional water molecules, forming a two-dimensional layer which serves as a potential template to simulate an aqueous interface in environmental conditions. Again, employing finite-temperature AIMD trajectories at the PBE+D2 level, we investigated the behaviour of both hydroxylated surface (HS) and the water-covered structure derived from it (known as HS+2ML). A full range of spectra, from VDOS to IR and VSF, is then calculated using the same methodology, as described above. This is the main focus of the second project, reported in Chapter 5. In this case, comparison between theoretical spectra and experimental data is definitely good. In particular, we underline the nature of high-frequency resonances observed above 3700 cm −1 in VSF experiments to be associated with surface OH-groups, known as “aluminols” which are a key fingerprint of the fully hydroxylated surface.
In the third and last project, which is presented in Chapter 6, the extension of VSF spectroscopy experiments to the time-resolved regime offered us the opportunity to investigate vibrational energy relaxation at the α-alumina / water interface. Specifically, using again DFT-based AIMD simulations, we simulated vibrational lifetimes for surface aluminols as experimentally detected via pump-probe VSF. We considered the water-covered HS model as a potential candidate to address this problem. The vibrational (IR) excitation and subsequent relaxation is performed by means of a non-equilibrium molecular dynamics scheme. In such a scheme, we specifically looked at the O-H stretching mode of surface aluminols. Afterwards, the analysis of non-equilibrium trajectories allows for an estimation of relaxation times in the order of 2-4 ps which are in overall agreement with measured ones.
The aim of this work has been to provide, within a consistent theoretical framework, a better understanding of vibrational spectroscopy and dynamics for water on the α-alumina(0001) surface,ranging from very low water coverage (similar to the UHV case) up to medium-high coverages, resembling the hydroxylated oxide in environmental moist conditions.
The present work is a compilation of three original research articles submitted (or already published) in international peer-reviewed venues of the field of speech science. These three articles address the topics of fundamental motor laws in speech and dynamics of corresponding speech movements:
1. Kuberski, Stephan R. and Adamantios I. Gafos (2019). "The speed-curvature power law in tongue movements of repetitive speech". PLOS ONE 14(3). Public Library of Science. doi: 10.1371/journal.pone.0213851.
2. Kuberski, Stephan R. and Adamantios I. Gafos (In press). "Fitts' law in tongue movements of repetitive speech". Phonetica: International Journal of Phonetic Science. Karger Publishers. doi: 10.1159/000501644
3. Kuberski, Stephan R. and Adamantios I. Gafos (submitted). "Distinct phase space topologies of identical phonemic sequences". Language. Linguistic Society of America.
The present work introduces a metronome-driven speech elicitation paradigm in which participants were asked to utter repetitive sequences of elementary consonant-vowel syllables. This paradigm, explicitly designed to cover speech rates from a substantially wider range than has been explored so far in previous work, is demonstrated to satisfy the important prerequisites for assessing so far difficult to access aspects of speech. Specifically, the paradigm's extensive speech rate manipulation enabled elicitation of a great range of movement speeds as well as movement durations and excursions of the relevant effectors. The presence of such variation is a prerequisite to assessing whether invariant relations between these and other parameters exist and thus provides the foundation for a rigorous evaluation of the two laws examined in the first two contributions of this work.
In the data resulting from this paradigm, it is shown that speech movements obey the same fundamental laws as movements from other domains of motor control do. In particular, it is demonstrated that speech strongly adheres to the power law relation between speed and curvature of movement with a clear speech rate dependency of the power law's exponent. The often-sought or reported exponent of one third in the statement of the law is unique to a subclass of movements which corresponds to the range of faster rates under which a particular utterance is produced. For slower rates, significantly larger values than one third are observed. Furthermore, for the first time in speech this work uncovers evidence for the presence of Fitts' law. It is shown that, beyond a speaker-specific speech rate, speech movements of the tongue clearly obey Fitts' law by emergence of its characteristic linear relation between movement time and index of difficulty. For slower speech rates (when temporal pressure is small), no such relation is observed. The methods and datasets obtained in the two assessment above provide a rigorous foundation both for addressing implications for theories and models of speech as well as for better understanding the status of speech movements in the context of human movements in general.
All modern theories of language rely on a fundamental segmental hypothesis according to which the phonological message of an utterance is represented by a sequence of segments or phonemes. It is commonly assumed that each of these phonemes can be mapped to some unit of speech motor action, a so-called speech gesture.
For the first time here, it is demonstrated that the relation between the phonological description of simple utterances and the corresponding speech motor action is non-unique. Specifically, by the extensive speech rate manipulation in the herein used experimental paradigm it is demonstrated that speech exhibits clearly distinct dynamical organizations underlying the production of simple utterances. At slower speech rates, the dynamical organization underlying the repetitive production of elementary /CV/ syllables can be described by successive concatenations of closing and opening gestures, each with its own equilibrium point. As speech rate increases, the equilibria of opening and closing gestures are not equally stable yielding qualitatively different modes of organization with either a single equilibrium point of a combined opening-closing gesture or a periodic attractor unleashed by the disappearance of both equilibria. This observation, the non-uniqueness of the dynamical organization underlying what on the surface appear to be identical phonemic sequences, is an entirely new result in the domain of speech. Beyond that, the demonstration of periodic attractors in speech reveals that dynamical equilibrium point models do not account for all possible modes of speech motor behavior.
Seit 2003 hat sich das politische Bild des Irak stark verändert. Dadurch begann der Prozess der Neugestaltung der irakischen Rechtsordnung. Die irakische Verfassung von 2005 legt erstmalig in der Geschichte des Irak den Islam und die Demokratie als zwei nebeneinander zu beachtende Grundprinzipien bei der Gesetzgebung fest. Trotz dieser signifikanten Veränderung im irakischen Rechtssystem und erheblicher Entwicklungen im internationalen Privat- und Zivilverfahrensrecht (IPR/IZVR) im internationalen Vergleich gilt die hauptsächlich im irakischen Zivilgesetzbuch (ZGB) von 1951 enthaltene gesetzliche Regelung des IPR/IZVR im Irak weiterhin. Deshalb entstand diese Arbeit für eine Reformierung des irakischen IPR/IZVR.
Die Arbeit gilt als erste umfassende wissenschaftliche Untersuchung, die sich mit dem jetzigen Inhalt und der zukünftigen Reformierung des irakischen internationalen Privatrecht- und Zivilverfahrensrechts (IPR/IZVR) beschäftigt.
Die Verfasserin vermittelt einen Gesamtüberblick über das jetzt geltende irakische internationale Privat- und Zivilverfahrensrecht mit gelegentlicher punktueller und stichwortartiger Heranziehung des deutschen, islamischen, türkischen und tunesischen Rechts, zeigt dessen Schwachstellen auf und unterbreitet entsprechende Reformvorschläge.
Wegen der besonderen Bedeutung des internationalen Vertragsrechts für die Wirtschaft im Irak und auch zum Teil für Deutschland gibt die Verfasserin einen genaueren Überblick über das irakische internationale Vertragsrecht und bekräftigt gleichzeitig dessen Reformbedürftigkeit.
Die Darstellung der wichtigen Entwicklungen im deutsch-europäischen, im traditionellen islamischen Recht und im türkischen und tunesischen internationalen Privat- und Zivilverfahrensrecht im zweiten Kapitel dienen als Grundlage, auf die bei der Reformierung des irakischen IPR/ IZVR zurück gegriffen werden kann. Da die Kenntnisse des islamischen Rechts nicht zwingend zum Rechtsstudium gehören, wird das islamische Recht dazu in Bezug auf seine Entstehung und die Rechtsquellen dargestellt.
Am Ende der Arbeit wird ein Entwurf eines föderalen Gesetzes zum internationalen Privatrecht im Irak katalogisiert, der sich im Rahmen der irakischen Verfassung gleichzeitig mit dem Islam und der Demokratie vereinbaren lässt.
Floral scent is an important way for plants to communicate with insects, but scent emission has been lost or strongly reduced during the transition from pollinator-mediated outbreeding to selfing. The shift from outcrossing to selfing is not only accompanied by scent loss, but also by a reduction in other pollinator-attracting traits like petal size and can be observed multiple times among angiosperms. These changes are summarized by the term selfing syndrome and represent one of the most prominent examples of convergent evolution within the plant kingdom. In this work the genus Capsella was used as a model to study convergent evolution in two closely related selfers with separate transitions to self-fertilization.
Compared to their outbreeding ancestor C. grandiflora, the emission of benzaldehyde as main compound of floral scent is lacking or strongly reduced in the selfing species C. rubella and C. orientalis. In C. rubella the loss of benzaldehyde was caused by mutations to cinnamate:CoA ligase CNL1, but the biochemical basis and evolutionary history of this loss remained unknown, together with the genetic basis of scent loss in C. orientalis. Here, a combination of plant transformations, in vitro enzyme assays, population genetics and quantitative genetics has been used to address these questions. The results indicate that CNL1 has been inactivated twice independently by point mutations in C. rubella, leading to a loss of benzaldehyde emission. Both inactivated haplotypes can be found around the Mediterranean Sea, indicating that they arose before the species´ geographical spread. This study confirmed CNL1 as a hotspot for mutations to eliminate benzaldehyde emission, as it has been suggested by previous studies. In contrast to these findings, CNL1 in C. orientalis remains active. To test whether similar mechanisms underlie the convergent evolution of scent loss in C. orientalis a QTL mapping approach was used and the results suggest that this closely related species followed a different evolutionary route to reduce floral scent, possibly reflecting that the convergent evolution of floral scent is driven by ecological rather than genetic factors.
In parallel with studying the genetic basis of repeated scent loss a method for testing the adaptive value of individual selfing syndrome traits was established. The established method allows estimating outcrossing rates with a high throughput of samples and detects successfully insect-mediated outcrossing events, providing major advantages regarding time and effort compared to other approaches. It can be applied to correlate outcrossing rates with differences in individual traits by using quasi-isogenic lines as demonstrated here or with environmental or morphological parameters.
Convergent evolution can not only be observed for scent loss in Capsella but also for the morphological evolution of petal size. Previous studies detected several QTLs underlying the petal size reduction in C. orientalis and C. rubella, some of them shared among both species. One shared QTL is PAQTL1 which might map to NUBBIN, a growth factor. To better understand the morphological evolution and genetic basis of petal size reduction, this QTL was studied. Mapping this QTL to a gene might identify another example for a hotspot gene, in this case for the convergent evolution of petal size.
Quantum field theory on curved spacetimes is understood as a semiclassical approximation of some quantum theory of gravitation, which models a quantum field under the influence of a classical gravitational field, that is, a curved spacetime. The most remarkable effect predicted by this approach is the creation of particles by the spacetime itself, represented, for instance, by Hawking's evaporation of black holes or the Unruh effect. On the other hand, these aspects already suggest that certain cornerstones of Minkowski quantum field theory, more precisely a preferred vacuum state and, consequently, the concept of particles, do not have sensible counterparts within a theory on general curved spacetimes. Likewise, the implementation of covariance in the model has to be reconsidered, as curved spacetimes usually lack any non-trivial global symmetry. Whereas this latter issue has been resolved by introducing the paradigm of locally covariant quantum field theory (LCQFT), the absence of a reasonable concept for distinct vacuum and particle states on general curved spacetimes has become manifest even in the form of no-go-theorems.
Within the framework of algebraic quantum field theory, one first introduces observables, while states enter the game only afterwards by assigning expectation values to them. Even though the construction of observables is based on physically motivated concepts, there is still a vast number of possible states, and many of them are not reasonable from a physical point of view. We infer that this notion is still too general, that is, further physical constraints are required. For instance, when dealing with a free quantum field theory driven by a linear field equation, it is natural to focus on so-called quasifree states. Furthermore, a suitable renormalization procedure for products of field operators is vitally important. This particularly concerns the expectation values of the energy momentum tensor, which correspond to distributional bisolutions of the field equation on the curved spacetime. J. Hadamard's theory of hyperbolic equations provides a certain class of bisolutions with fixed singular part, which therefore allow for an appropriate renormalization scheme.
By now, this specification of the singularity structure is known as the Hadamard condition and widely accepted as the natural generalization of the spectral condition of flat quantum field theory. Moreover, due to Radzikowski's celebrated results, it is equivalent to a local condition, namely on the wave front set of the bisolution. This formulation made the powerful tools of microlocal analysis, developed by Duistermaat and Hörmander, available for the verification of the Hadamard property as well as the construction of corresponding Hadamard states, which initiated much progress in this field. However, although indispensable for the investigation in the characteristics of operators and their parametrices, microlocal analyis is not practicable for the study of their non-singular features and central results are typically stated only up to smooth objects. Consequently, Radzikowski's work almost directly led to existence results and, moreover, a concrete pattern for the construction of Hadamard bidistributions via a Hadamard series. Nevertheless, the remaining properties (bisolution, causality, positivity) are ensured only modulo smooth functions.
It is the subject of this thesis to complete this construction for linear and formally self-adjoint wave operators acting on sections in a vector bundle over a globally hyperbolic Lorentzian manifold. Based on Wightman's solution of d'Alembert's equation on Minkowski space and the construction for the advanced and retarded fundamental solution, we set up a Hadamard series for local parametrices and derive global bisolutions from them. These are of Hadamard form and we show existence of smooth bisections such that the sum also satisfies the remaining properties exactly.
Die vorliegende Dissertation zielt generell darauf ab, die Anwendung der dialektischen Methodologie auf den Bereich der Sprachphilosophie zu rechtfertigen und eine systematische Bearbeitung eines begrenzten Teils der Sprachphilosophie mithilfe der Dialektik durchzuführen. Um diese Herangehensweise, die in der Forschung kaum oder gar nicht vertreten ist, aufzuklären und festzustellen, werde ich zuerst auf die philosophischen Überlegungen von zwei Autoren zurückgreifen: Hegel und Wittgenstein.
Hegel und Wittgenstein sind, auf den ersten Blick, Autoren, die kaum Gemeinsamkeiten haben, außer dass sie sich beide mit der Philosophie als Fach beschäftigt und unvermeidlich ein gemeinschaftliches Thema, die Sprache, behandelt haben, wobei jedoch weder eine inhaltliche noch eine methodologische Verbindung hervorgehoben werden könnte. Die erste Voraussetzung dieser Dissertation, in Bezug auf die Geschichte der Idee, besteht darin, darauf hinzudeuten, dass der hegelsche Geistesbegriff und Wittgensteins Lebensform zwei Ansätze und Resultat einer philosophischen Bemühung sind, die gemeinsam die notwendige Auflösung bzw. Überwindung skeptischer Argumentation vornehmen. Tatsächlich hat Wittgenstein in seinen Philosophischen Untersuchungen eine Argumentation entwickelt, die als „Paradox des Regelfolgens“ bezeichnet und in der sekundären Literatur (hauptsächlich bei Kripke) als eine Art skeptische Argumentation betrachtet wurde. Demnach wird Wittgensteins Theorie der Sprache entweder als eine Auflösung dieses Skeptizismus oder einfach als ein skeptischer Text selbst ausgelegt (Brandom). Das erste Ziel meiner Dissertation besteht darin, zu zeigen, dass dieses Paradox als skeptische Argumentation allerdings unvollständig geblieben ist dass dieses Paradox als der erster entscheidender Moment zu der höchsten Form der skeptischen Herausforderung, der Antinomie, betrachtet werden kann. Eine vollständige skeptische Argumentation heißt, dass die alleinige Auflösung des Paradoxes, der Dispositionalismus und die Negation dieser Theorie, beide beweisbar sind. Ich werde also versuchen, aus der in den PU dargestellten Auflösung des Paradoxes des Regelfolgens die Vervollständigung einer Antinomie des Begriffes der Normativität in Bezug auf die Sprachregeln festzulegen, ähnlich der von Kant entwickelten kosmologischen Antinomie (Thesis cum Antithesis). Das zweite Ziel meiner Dissertation besteht folglich darin, zu zeigen, 1. dass die kantische Auflösung der Antinomie unwirksam bezüglich der Antinomie der Normativität ist, 2. dass diese Antinomie eine notwendige Auseinandersetzung mit einem radikalen Skeptizismus bedeutet und dass wir logisch gezwungen sind, nicht nur irgendeine Theorie der Sprachphilosophie neu zu bestimmen, sondern unsere Methodologie – das heißt die Anwendung der üblichen Normen der Rationalität – selbst grundsätzlich tiefer gehend in Frage zu stellen, und 3. dass die hegelsche Dialektik sich als die methodologische Auflösung einer solchen radikalen skeptischen Herausforderung bzw. als die Auflösung einer Antinomie überhaupt ergibt. Anlässlich dieser methodologischen Revidierung wird auf die hegelsche Dialektik zurückgegriffen.
Dennoch begrenzt sich der Zweck dieser Dissertation nicht darauf, eine Interpretation von Hegels Dialektik oder eine Überwindung von Wittgensteins Lebensform darzustellen, vielmehr geht es darum, auf die Problematik und die Grundsätze des Begriffs der Lebensform bzw. des theoretischen Geistes zurückzugreifen und kraft Hegels Dialektik darüber hinauszuführen, um den Platz und die Funktion der Sprache besser zu verstehen. Diese Arbeit erfolgt vielmehr im Rahmen eines wissenschaftlichen Projekts, oder anders gesagt, sie nutzt die methodologischen Resultate von zwei Autoren der Philosophie, um ein wissenschaftliches Programm vorzustellen. Der Anspruch dieser Arbeit ist dementsprechend, durch das Zurückgreifen auf Hegels Dialektik eine neue Erkenntnis über die Sprache zu gewinnen, wobei die beiden kontradiktorischen Momente der Kognition – die Normativität, die durch das Bewusstsein erfolgt und diejenige, die durch Dispositionen erfolgt –, konstruktiv verbinden sind. Der konkrete Gewinn dieser Methodologie ist es demnach, eine Sprachphilosophie überhaupt als System festlegen zu können, ein System, das es ermöglicht, sprachliche Phänomene in all ihren Aspekten in kohärenter Weise zu fassen. Inhaltlich betrachtet zielt dieses Programm darauf ab, die allgemeine Stufe des Begriffs der Sprache als Moment des Begriffs des Geistes dialektisch abzuleiten, d. h. den richtigen Sinn der Sprache festzulegen. Eine vollständige Bearbeitung der Sprachphilosophie mithilfe der Dialektik konnte ich allerdings nicht durchführen, und der Umfang der mithilfe der Dialektik hergeleiteten Sprachkategorien begrenzt sich auf die Lehre der Einbildungskraft, die die Lehre der allgemeinen Semiologie und der Grammatik einschließt.
Hyperspectral remote sensing of the spatial and temporal heterogeneity of low Arctic vegetation
(2019)
Arctic tundra ecosystems are experiencing warming twice the global average and Arctic vegetation is responding in complex and heterogeneous ways. Shifting productivity, growth, species composition, and phenology at local and regional scales have implications for ecosystem functioning as well as the global carbon and energy balance. Optical remote sensing is an effective tool for monitoring ecosystem functioning in this remote biome. However, limited field-based spectral characterization of the spatial and temporal heterogeneity limits the accuracy of quantitative optical remote sensing at landscape scales. To address this research gap and support current and future satellite missions, three central research questions were posed:
• Does canopy-level spectral variability differ between dominant low Arctic vegetation communities and does this variability change between major phenological phases?
• How does canopy-level vegetation colour images recorded with high and low spectral resolution devices relate to phenological changes in leaf-level photosynthetic pigment concentrations?
• How does spatial aggregation of high spectral resolution data from the ground to satellite scale influence low Arctic tundra vegetation signatures and thereby what is the potential of upcoming hyperspectral spaceborne systems for low Arctic vegetation characterization?
To answer these questions a unique and detailed database was assembled. Field-based canopy-level spectral reflectance measurements, nadir digital photographs, and photosynthetic pigment concentrations of dominant low Arctic vegetation communities were acquired at three major phenological phases representing early, peak and late season. Data were collected in 2015 and 2016 in the Toolik Lake Research Natural Area located in north central Alaska on the North Slope of the Brooks Range. In addition to field data an aerial AISA hyperspectral image was acquired in the late season of 2016. Simulations of broadband Sentinel-2 and hyperspectral Environmental and Mapping Analysis Program (EnMAP) satellite reflectance spectra from ground-based reflectance spectra as well as simulations of EnMAP imagery from aerial hyperspectral imagery were also obtained.
Results showed that canopy-level spectral variability within and between vegetation communities differed by phenological phase. The late season was identified as the most discriminative for identifying many dominant vegetation communities using both ground-based and simulated hyperspectral reflectance spectra. This was due to an overall reduction in spectral variability and comparable or greater differences in spectral reflectance between vegetation communities in the visible near infrared spectrum.
Red, green, and blue (RGB) indices extracted from nadir digital photographs and pigment-driven vegetation indices extracted from ground-based spectral measurements showed strong significant relationships. RGB indices also showed moderate relationships with chlorophyll and carotenoid pigment concentrations. The observed relationships with the broadband RGB channels of the digital camera indicate that vegetation colour strongly influences the response of pigment-driven spectral indices and digital cameras can track the seasonal development and degradation of photosynthetic pigments.
Spatial aggregation of hyperspectral data from the ground to airborne, to simulated satel-lite scale was influenced by non-photosynthetic components as demonstrated by the distinct shift of the red edge to shorter wavelengths. Correspondence between spectral reflectance at the three scales was highest in the red spectrum and lowest in the near infra-red. By artificially mixing litter spectra at different proportions to ground-based spectra, correspondence with aerial and satellite spectra increased. Greater proportions of litter were required to achieve correspondence at the satellite scale.
Overall this thesis found that integrating multiple temporal, spectral, and spatial data is necessary to monitor the complexity and heterogeneity of Arctic tundra ecosystems. The identification of spectrally similar vegetation communities can be optimized using non-peak season hyperspectral data leading to more detailed identification of vegetation communities. The results also highlight the power of vegetation colour to link ground-based and satellite data. Finally, a detailed characterization non-photosynthetic ecosystem components is crucial for accurate interpretation of vegetation signals at landscape scales.
The unprecedented increase in atmospheric concentrations of carbon dioxide (CO2) and other greenhouse gases (GHG) by anthropogenic activities since the Industrial Revolution impacts on various earth system processes, commonly referred to as `climate change´ (CC). CC faces aquatic ecosystems with extreme abiotic perturbations that potentially alter the interrelations between functional autotrophic and heterotrophic plankton groups. These relations, however, modulate biogeochemical cycling and mediate the functioning of aquatic ecosystems as C sources or sinks to the atmosphere. The aim of this thesis was therefore to investigate how different aspects of CC influence community composition and functioning of pelagic heterotrophic bacteria. These organisms constitute a major component of biogeochemical cycling and largely determine the balance between autotrophic and heterotrophic processes.
Due to the vast amount of potential CC impacts, this thesis focuses on the following two aspects: (1) Increased exchange of CO2 across the atmosphere-water interface and reaction of CO2 with seawater leads to profound shifts in seawater carbonate chemistry, commonly termed as `ocean acidification´ (OA), with consequences for organism physiology and the availability of dissolved inorganic carbon (DIC) in seawater. (2) The increase in atmospheric GHG concentration impacts on the efficiency with which the Earth cools to space, affecting global surface temperature and climate. With ongoing CC, shifts in frequency and severity of episodic weather events, such as storms, are expected that in particular might affect lake ecosystems by disrupting thermal summer stratification. Both aspects of CC were studied at the ecosystem-level in large-volume mesocosm experiments by using the Kiel Off-shore Mesocosms for Future Ocean Simulations (KOSMOS) deployed at different coastal marine locations, and the LakeLab facility in Lake Stechlin.
We evaluated the impact of OA on heterotrophic bacterial metabolism in a brackish coastal ecosystem during low-nutrient summer months in the Baltic Sea. There are several in situ experiments that already assessed potential OA-induced changes in natural plankton communities at diverse spatial and seasonal conditions. However, most studies were performed at high phytoplankton biomass conditions, partly provoked by nutrient amendments. Our study highlights potential OA effects at low-nutrient conditions that are representative for most parts of the ocean and of particular interest in current OA research. The results suggest that during extended periods at low-nutrient concentrations, increasing pCO2 levels indirectly impact the growth balance of heterotrophic bacteria via trophic bacteria-phytoplankton interactions and shift the ecosystem to a more autotrophic system.
Further work investigated how OA affects heterotrophic bacterial dissolved organic matter (DOM) transformation in two mesocsom studies, performed at different nutrient conditions. We observed similar succession patterns for individual compound pools during a phytoplankton bloom and subsequent accumulation of these compounds irrespective of the pCO2 treatment. Our results indicate that OA-induced changes in the dynamics of bacterial DOM transformation and potential impacts on DOM quality are unlikely. In addition, there have been no indications that in dependence of nutrient conditions, different amounts of photosynthetic organic matter are channelled into the more recalcitrant DOM pool. This provides novel insights into the general dynamics of the marine DOM pool.
A fourth enclosure experiment in oligo-mesotrophic Lake Stechlin assessed the impact of a severe summer storm on lake bacterial communities during thermal stratification by artificially mixing. Mixing disrupted and lowered the thermocline, increasing the upper mixed layer and substantially changed water physical-chemical variables. Deep water entrainment and associated changes in water physical-chemical variables significantly affected relative bacterial abundances for about one week. Afterwards a pronounced cyanobacterial bloom developed in response to mixing which affected community assembly of heterotrophic bacteria. Colonization and mineralization of senescent phytoplankton cells by heterotrophic bacteria largely determined C-sequestration to the sediment. About six weeks after mixing, bacterial communities and measured activity parameters converged to control conditions. As such, summer storms have the potential to affect bacterial communities for a prolonged period during summer stratification. The results highlight effects on community assembly and heterotrophic bacterial metabolism that are associated to entrainment of deep water into the mixed water layer and assess consequences of an episodic disturbance event for the coupling between bacterial metabolism and autochthonous DOM production in large volume clear-water lakes.
Altogether, this doctoral thesis reveales substantial sensitivities of heterotrophic bacterial metabolism and community structure in response to OA and a simulated summer storm event, which should be considered when assessing the impact of climate change on marine and lake ecosystems.
The trace gases CO2 and CH4 pertain to the most relevant greenhouse gases and are important exchange fluxes of the global carbon (C) cycle. Their atmospheric quantity increased significantly as a result of the intensification of anthropogenic activities, such as especially land-use and land-use change, since the mid of the 18th century. To mitigate global climate change and ensure food security, land-use systems need to be developed, which favor reduced trace gas emissions and a sustainable soil carbon management. This requires the accurate and precise quantification of the influence of land-use and land-use change on CO2 and CH4 emissions. A common method to determine the trace gas dynamics and C sink or source function of a particular ecosystem is the closed chamber method. This method is often used assuming that accuracy and precision are high enough to determine differences in C gas emissions for e.g., treatment comparisons or different ecosystem components.
However, the broad range of different chamber designs, related operational procedures and data-processing strategies which are described in the scientific literature contribute to the overall uncertainty of closed chamber-based emission estimates. Hence, the outcomes of meta-analyses are limited, since these methodical differences hamper the comparability between studies. Thus, a standardization of closed chamber data acquisition and processing is much-needed.
Within this thesis, a set of case studies were performed to: (I) develop standardized routines for an unbiased data acquisition and processing, with the aim of providing traceable, reproducible and comparable closed chamber based C emission estimates; (II) validate those routines by comparing C emissions derived using closed chambers with independent C emission estimates; and (III) reveal processes driving the spatio-temporal dynamics of C emissions by developing (data processing based) flux separation approaches.
The case studies showed: (I) the importance to test chamber designs under field conditions for an appropriate sealing integrity and to ensure an unbiased flux measurement. Compared to the sealing integrity, the use of a pressure vent and fan was of minor importance, affecting mainly measurement precision; (II) that the developed standardized data processing routines proved to be a powerful and flexible tool to estimate C gas emissions and that this tool can be successfully applied on a broad range of flux data sets from very different ecosystem; (III) that automatic chamber measurements display temporal dynamics of CO2 and CH4 fluxes very well and most importantly, that they accurately detect small-scale spatial differences in the development of soil C when validated against repeated soil inventories; and (IV) that a simple algorithm to separate CH4 fluxes into ebullition and diffusion improves the identification of environmental drivers, which allows for an accurate gap-filling of measured CH4 fluxes.
Overall, the proposed standardized data acquisition and processing routines strongly improved the detection accuracy and precision of source/sink patterns of gaseous C emissions. Hence, future studies, which consider the recommended improvements, will deliver valuable new data and insights to broaden our understanding of spatio-temporal C gas dynamics, their particular environmental drivers and underlying processes.
A reliable inference of networks from data is of key interest in many scientific fields. Several methods have been suggested in the literature to reliably determine links in a network. These techniques rely on statistical methods, typically controlling the number of false positive links, but not considering false negative links. In this thesis new methodologies to improve network inference are suggested. Initial analyses demonstrate the impact of falsepositive and false negative conclusions about the presence or absence of links on the resulting inferred network. Consequently, revealing the importance of making well-considered choices leads to suggest new approaches to enhance existing network reconstruction methods.
A simulation study, presented in Chapter 3, shows that different values to balance false positive and false negative conclusions about links should be used in order to reliably estimate network characteristics. The existence of type I and type II errors in the reconstructed network, also called biased network, is accepted. Consequently, an analytic method that describes the influence of these two errors on the network structure is explored. As a result of this analysis, an analytic formula of the density of the biased vertex degree distribution is found (Chapter 4).
In the inverse problem, the vertex degree distribution of the true underlying network is analytically reconstructed, assuming the probabilities of type I and type II errors. Chapters 4-5 show that the method is robust to incorrect estimates of α and β within reasonable limits. In Chapter 6, an iterative procedure to enhance this method is presented in the case of large errors on the estimates of α and β.
The investigations presented so far focus on the influence of false positive and false negative links on the network characteristics. In Chapter 7, the analysis is reversed - the study focuses on the influence of network characteristics on the probability of type I and type II errors, in the case of networks of coupled oscillators. The probabilities of α and β are influenced by the shortest path length and the detour degree, respectively. These results have been used to improve the network reconstruction, when the true underlying network is not known a priori, introducing a novel and advanced concept of threshold.
Carbonfasern haben sich in der Luft- und Raumfahrt etabliert und gewinnen in Alltagsanwendungen wie dem Automobilbereich, Windkraft- und Sportbereich durch ihre hohen Zugfestigkeiten, insbesondere ihrer hohen E-Moduli, und ihrer geringen Dichte immer mehr an Bedeutung. Auf Grund ihrer hohen Kosten, welche sich zur Hälfte aus der Precursorherstellung, inklusive seiner Synthese und seinem Verspinnprozess, dem Lösungsspinnverfahren, ergeben, erhalten zunehmend alternative und schmelzspinnbare Precursoren Interesse. Für die Carbonfaserherstellung wird fast ausschließlich Polyacrylnitril (PAN) verwendet, das vor dem Schmelzen irreversible exotherme Zyklisierungsreaktionen aufweist, welchen sich seine Zersetzung anschließt. Eine Möglichkeit der Reduzierung der Schmelztemperatur von Polymeren ist die Einbringung von Comonomeren zur Erhöhung des freien Volumens und die Reduzierung der intermolekularen Wechselwirkungen als interne Weichmacher. Wie am Fraunhofer IAP gezeigt wurde, kann mittels 2-Methoxyethylacrylat (MEA) die Schmelztemperatur zu neuartigen PAN-basierten Precursoren verringert werden. Um den PAN-co-MEA-Precursor für die nachfolgenden Prozessschritte der Carbonfaserherstellung zu verwenden, müssen die thermoplastischen Fasern in thermisch stabile Fasern ohne thermoplastisches Verhalten überführt werden. Es wurde ein neuer Prozessschritt (Prästabilisierung) eingeführt, welcher unter alkalischen Bedingungen zur Abspaltung der Comonomerseitenkette führt. Neben der Esterhydrolyse finden Reaktionen statt, welche an diesem Material noch nicht hinreichend untersucht wurden. Weiterhin stellt sich die Frage nach der Kinetik der Prästabilisierung und der Ermittlung einer geeigneten Prozessführung.
Hierzu wurde die Prästabilisierung in den Labormaßstab überführt und die möglichen Zusammensetzungen des aus DMSO und einer KOH-Lösung bestehenden Reaktionsmediums evaluiert. Weiterhin wurde die Behandlung bei verschiedenen Prästabilisierungszeiten von maximal 30 min und Temperaturen von 40, 50 und 60 °C durchgeführt, um primär mittels NMR-Spektroskopie die chemischen Strukturänderungen aufzuklären. Die Esterhydrolyse des Comonomers, welche zur Abspaltung des 2-Methoxyethanols führt, wurde mittels 1H-NMR-spektroskopischer Untersuchungen detektiert.
Es wurde ein Modell aufgestellt, das die chemisch-physikalischen Strukturänderungen während der Prästabilisierung aufzeigt. Die zuerst ablaufende Reaktion ist die Esterhydrolyse am Comonomer, welche vom Faserrand nach innen verläuft und durch die Präsenz des DMSO in Kombination mit der KOH-Lösung (Superbase) initiiert wird. Der zeitliche Reaktionsverlauf der Esterhydrolyse kann in drei Bereiche eingeteilt werden. Der erste Bereich ab dem Prästabilisierungsbeginn wird durch die Diffusion der basischen Anionen in die Faser, der zweite Bereich durch die Reaktion an der Estergruppe des Comonomers und der dritte Bereich durch letzte Reaktionen im Faserinneren und diffusiven Prozessen der Produkte und Edukte charakterisiert. Der zweite Bereich kann mit einer Reaktion pseudo 1. Ordnung abgebildet werden, da in diesem Bereich bereits eine ausreichende Diffusion der Edukte in die Faser stattgefunden hat. Bei 50 °C spielt die Diffusion im ersten Bereich im Vergleich zur Reaktion eine untergeordnete Rolle. Mit Erhöhung der Temperatur auf 60 °C kann eine im Verhältnis geringere Diffusions- als Reaktionsgeschwindigkeit beobachtet werden. Die Nebenreaktionen wurden mittels 13C-CP/MAS-NMR-spektroskopischen, elementaranlaytischen Untersuchungen sowie Doppelbrechungsmessungen charakterisiert. Während der alkalischen Esterhydrolyse beginnt die Reduzierung der Nitrilgruppen unter der Bildung von primären Carbonsäureamiden und Carbonsäuren. Zur Beschreibung dieser Umsetzung wurde eine Methode entwickelt, welche die Addition von 13C-CP/MAS-NMR-Spektren der Modellsubstanzen PAN, PAM und PAA beinhaltet. Weitere stattfindende Reaktionen sind die Bildung von konjugierten Doppelbindungen, welche insbesondere auf eine Zyklisierung der Nitrile hinweisen. Die nasschemisch initiierte Zyklisierung der Nitrilgruppen kann zu kürzeren Stabilisierungszeiten und einem besser kontrollierbaren Stabilisierungsprozess durch geringere Wärmefreisetzung und schlussendlich zu einer Kostenersparnis des gesamten Verfahrens führen. Die Umsetzung der Nitrilgruppen konnte mit einer Reaktion pseudo 1. Ordnung gut abgebildet werden. DMSO initiiert die Esterhydrolyse, wobei die KOH-Konzentration einen höheren Einfluss auf die Reaktionsgeschwindigkeit der Ester- und Nitrilhydrolyse als die DMSO-Konzentration besitzt. Beide Reaktionen zeigen eine vergleichbare Abhängigkeit von der Temperatur. Die Erhöhung der Prästabilisierungszeit und der KOH- bzw. DMSO-Konzentration führt zur Migration niedermolekularer Bestandteile des Fasermaterials an die Oberfläche und der Bildung punktueller Ablagerungen bis hin zu miteinander verbundenen Einzelfasern. Eine weitere Erhöhung der Prästabilisierungszeit bzw. der Konzentration führt zu einem steigenden Carbonsäureanteil und zur Quellung des Fasermaterials, wodurch die Ablagerungen in das Reaktionsmedium diffundieren. Die Ablagerungen enthalten Chlor, welches durch den Waschvorgang mit HCl in das Materialsystem gelangt ist und durch Parameteranpassungen reduziert wurde. Die schmelzbaren Fasern konnten durch die Prästabilisierung erfolgreich über eine Kern-Mantel-Struktur in nicht-thermoplastische Fasern überführt werden.
Zur Ermittlung eines geeigneten Prozessfensters für nachfolgende thermische Beanspruchungen der prästabilisierten Fasern wurden drei Kriterien identifiziert, anhand welcher die Evaluation erfolgte. Das erste Kriterium beinhaltet die Notwendigkeit der vollständigen Aufhebung der thermoplastischen Eigenschaft der Fasern. Als zweites Kriterium diente die Fasermorphologie. Anhand von REM-Aufnahmen wurden Faserbündel mit separierten Einzelfasern ohne Ablagerungen für die nachfolgende Stabilisierung ausgewählt. Das dritte Kriterium bezieht sich auf eine möglichst geringe Umsetzung der Nitrilgruppen, um Prästabilisierungsbedingungen mit Nebenreaktionen zu vermeiden.
Aus den Untersuchungen konnte eine Prästabilisierungstemperatur von 60 °C als geeignet identifiziert werden. Weiterhin führen hoch alkalische Zusammensetzungen des Reaktionsmediums mit KOH-Konzentrationen von 1, 1,5 und 2 M, vorzugsweise 1,5 M und 50 vol% DMSO mit Reaktionszeiten von unter 10 min zu geeigneten Fasern. Ein MEA-Anteil unterhalb von 2 mol% bewirkt eine Überführung in die Unschmelzbarkeit. Thermisch stabile und für die nachfolgende Stabilisierung geeignete Fasern besitzen weiterhin 68 – 80 mol% Nitrilgruppen, 20 – 25 mol% Carbonsäuren, bis zu 15 mol% primäre Carbonsäureamide und zyklisierte Strukturen.
Sin pragmática no sería posible la comunicación, puesto que no podríamos interpretar enunciados lingüísticos. A cualquier aprendiente de una lengua que no domina, no le basta con ser competente lingüísticamente, puesto que su fin es comunicarse con otras personas y en contextos determinados. Solo una enseñanza que facilite la habilidad de producir y comprender enunciados para realizar actos de lengua, seleccionando los más apropiados para un contexto determinado, podrá preciarse de ser eficiente.
El trabajo que aquí se presenta pretende dar a conocer a la comunidad científica y, en especial, a los y las involucradas directa e indirectamente en el proceso de enseñanza, el concepto de pragmática verbal y contrastarlo con otros como gramática, cultura o interculturalidad, así como concienciarlos de la importancia y de la necesidad imperiosa del establecimiento de la pragmática como disciplina relevante en el proceso comunicativo y, en especial, de su inclusión sistemática y manifiesta en los libros de texto de español como lengua extranjera elaborados para el contexto escolar. Para ello se investiga la presencia de elementos pragmáticos y el fomento de la competencia pragmática en libros de texto para principiantes, por ser estos el material utilizado por excelencia en las escuelas y por su relevancia a la hora de especificar contenidos, tipo de progresión y metodología.
L’extériorisation de toute communication est assujettie à un mode d’accès du locuteur aux informations véhiculées. Les constatations faites de nos données prouvent que tous les huit verbes étudiés traduisent des mécanismes d’acquisition des connaissances que nous avons appelés en emprunt à (Vogeleer, 1995 :92) « l’accès cognitif au savoir ». C’est cette valeur intrinsèque qui vaut à ces termes la dénomination de verbes médiatifs. En d’autres mots, ce sont des éléments qui explicitent des processus d’accès du locuteur au savoir. Une source du savoir qui peut être directe (la vue, le touché, l’ouïe, l’odorat…) ou indirecte (ouï-dire) et surtout inférée. Nous entendons par inférence un processus d’analyse et de mise en relation d’éléments (prémisses), lesquelles permettent de tirer une conclusion par déduction, induction ou par abduction. Et selon que lesdites prémisses tendent à être plus ou moins fiables, ces processus inférentiels impliqueront des valeurs épistémiques à des degrés divers.
Sur le plan rhétorico-syntaxique, nos analyses ont montré tous les verbes cognitifs (VC) de cette étude exigent l’occurrence d’autres constituants (actants) phrastiques qu’ils régissent. C’est grâce à cette valence verbale qu’ils gardent un pouvoir rectionnel dans les constructions asyndétiques. Ce sont donc les matrices des éléments sur lesquels ils se rapportent. Quant au cinétisme de ces verbes, il possède une fonction rhétorique et syntaxique. En effet, cet agencement particulier et souvent perturbant permet de traduire l’expression d’une figure de syntaxe à effet rhétorique : l’hyperbate. Une construction atypique qui, à travers les agencements anticonformistes, donne un sens de regressivité à l’énoncé et confère une saillance à des termes mis ce fait en exergue.
Light-induced pH cycle
(2019)
Background Many biochemical reactions depend on the pH of their environment and some are strongly accelerated in an acidic surrounding. A classical approach to control biochemical reactions non-invasivly is by changing the temperature. However, if the pH could be controlled by optical means using photo-active chemicals, this would mean to be able to accelerate suitable biochemical reactions. Optically switching the pH can be achieved by using photoacids. A photoacid is a molecule with a functional group that releases a proton upon irradiation with the suitable wavelength, acidifying the environmental aqueous surrounding. A major goal of this work was to establish a non-invasive method of optically controlling the pH in aqueous solutions, offering the opportunity to enhance the known chemical reactions portfolio. To demonstrate the photo-switchable pH cycling we chose an enzymatic assay using acid phosphatase, which is an enzyme with a strong pH dependent activity.
Results In this work we could demonstrate a light-induced, reversible control of the enzymatic activity of acid phosphatase non-invasivly. To successfully conduct those experiments a high power LED array was designed and built, suitable for a 96 well standard microtiter plate, not being commercially available. Heat management and a lateral ventilation system to avoid heat accumulation were established and a stable light intensity achieved. Different photoacids were characterised and their pH dependent absorption spectra recorded. By using the reversible photoacid G-acid as a proton donor, the pH can be changed reversibly using high power UV 365 nm LEDs. To demonstrate the pH cycling, acid phosphatase with hydrolytic activity under acidic conditions was chosen. An assay using the photoacid together with the enzyme was established, also providing that G-acid does not inhibit acid phosphatase. The feasibility of reversibly regulating the enzyme’s pH dependent activity by optical means was demonstrated, by controlling the enzymatic activity with light. It was demonstrated that the enzyme activity depends on the light exposure time only. When samples are not illuminated and left in the dark, no enzymatic activity was recorded. The process can be rapidly controlled by simply switching the light on and off and should be applicable to a wide range of enzymes and biochemical reactions.
Conclusions Reversible photoacids offer a light-dependent regulation of pH, making them extremely attractive for miniaturizable, non-invasive and time-resolved control of biochemical reactions. Many enzymes have a sharp pH dependent activity, thus the established setup in this thesis could be used for a versatile enzyme portfolio. Even though the demonstrated photo-switchable strategy could also be used for non-enzymatic assays, greatly facilitating the assay establishment. Photoacids have the potential for high throughput methods and automation. We demonstrated that it is possible to control photoacids using commonly available LEDs, making their use in highly integrated devices and instruments more attractive. The successfully designed 96 well high power UV LED array presents an opportunity for general combinatorial analysis in e.g. photochemistry, where a high light intensity is needed for the investigation of various reactions.
Interlocutors typically link their utterances to the discourse environment and enrich communication by linguistic (e.g., information packaging) and extra-linguistic (e.g., eye gaze, gestures) means to optimize information transfer. Psycholinguistic studies underline that ‒for meaning computation‒ listeners profit from linguistic and visual cues that draw their focus of attention to salient information. This dissertation is the first work that examines how linguistic compared to visual salience cues influence sentence comprehension using the very same experimental paradigms and materials, that is, German subject-before-object (SO) and object-before-subject (OS) sentences, across the two cue modalities. Linguistic salience was induced by indicating a referent as the aboutness topic. Visual salience was induced by implicit (i.e., unconscious) or explicit (i.e., shared) manipulations of listeners’ attention to a depicted referent.
In Study 1, a selective, facilitative impact of linguistic salience on the context-sensitive OS word order was found using offline comprehensibility judgments. More precisely, during online sentence processing, this impact was characterized by a reduced sentence-initial Late positivity which reflects reduced processing costs for updating the current mental representation of discourse. This facilitative impact of linguistic salience was not replicated by means of an implicit visual cue (Study 2) shown to modulate word order preferences during sentence production. However, a gaze shift to a depicted referent as an indicator of shared attention eased sentence-initial processing similar to linguistic salience as revealed by reduced reading times (Study 3). Yet, this cue did not modulate the strong subject-antecedent preference during later pronoun resolution like linguistic salience. Taken together, these findings suggest a significant impact of linguistic and visual salience cues on sentence comprehension, which substantiates that both the information delivered via language and via the visual environment is integrated into the mental representation of the discourse; but, the way how salience is induced is crucial to its impact.
The goal of this thesis is to broaden the empirical basis for a better, comprehensive understanding
of massive star evolution, star formation and feedback at low metallicity. Low metallicity massive stars are a key to understand the early universe. Quantitative information on metal-poor massive stars was sparse before. The quantitative spectroscopic studies of massive star populations associated with large-scale ISM structures were not performed at low metallicity before, but are important to investigate star-formation histories and feedback in detail. Much of this work relies on spectroscopic observations with VLT-FLAMES of ~500 OB stars in the Magellanic Clouds. When available, the optical spectroscopy was complemented by UV spectra from the HST, IUE, and FUSE archives. The two representative young stellar populations that have been studied are associated with the superbubble N 206 in the Large Magellanic Cloud (LMC) and with the supergiant shell SMC-SGS 1 in the Wing of the Small Magellanic Cloud (SMC), respectively. We performed spectroscopic analyses of the massive stars using the nonLTE Potsdam Wolf-Rayet (PoWR) model atmosphere code. We estimated the stellar, wind, and feedback parameters of the individual massive stars and established their statistical distributions.
The mass-loss rates of N206 OB stars are consistent with theoretical expectations for LMC metallicity. The most massive and youngest stars show nitrogen enrichment at their surface and are found to be slower rotators than the rest of the sample. The N 206 complex has undergone star formation episodes since more than 30 Myr, with a current star formation rate higher than average in the LMC. The spatial age distribution of stars across the complex possibly indicates triggered star formation due to the expansion of the superbubble. Three very massive, young Of stars in the region dominate the ionizing and mechanical feedback among hundreds of other OB stars in the sample. The current stellar wind feedback rate from the two WR stars in the complex is comparable to that released by the whole OB sample. We see only a minor fraction of this stellar wind feedback converted into X-ray emission. In this LMC complex, stellar winds and supernovae equally contribute to the total energy feedback, which eventually powered the central superbubble. However, the total energy input accumulated over the time scale of the superbubble significantly exceeds the observed energy content of the complex. The lack of energy along with the morphology of the complex suggests a leakage of hot gas from the superbubble.
With a detailed spectroscopic study of massive stars in SMC-SGS 1, we provide the stellar and wind parameters of a large sample of OB stars at low metallicity, including those in the lower mass-range. The stellar rotation velocities show a broad, tentatively bimodal distribution, with Be stars being among the fastest. A few very luminous O stars are found close to the main sequence, while all other, slightly evolved stars obey a strict luminosity limit. Considering additional massive stars in evolved stages, with published parameters and located all over the SMC, essentially confirms this picture. The comparison with single-star evolutionary tracks suggests a dichotomy in the fate of massive stars in the SMC. Only stars with an initial mass below 30 solar masses seem to evolve from the main sequence to the cool side of the HRD to become a red supergiant and to explode as type II-P supernova. In contrast, more massive stars appear to stay always hot and might evolve quasi chemically homogeneously, finally collapsing to relatively massive black holes. However, we find no indication that chemical mixing is correlated with rapid rotation. We measured the key parameters of stellar feedback and established the links between the rates of star formation and supernovae. Our study demonstrates that in metal-poor environments stellar feedback is dominated by core-collapse supernovae in combination with winds and ionizing radiation supplied by a few of the most massive stars. We found indications of the stochastic mode of star formation, where the resulting stellar population is fully capable of producing large-scale structures such as the supergiant shell SMC-SGS 1 in the Wing. The low level of feedback in metal-poor stellar populations allows star formation episodes to persist over long timescales.
Our study showcases the importance of quantitative spectroscopy of massive stars with adequate stellar-atmosphere models in order to understand star-formation, evolution, and feedback. The stellar population analyses in the LMC and SMC make us understand that massive stars and their impact can be very different depending on their environment. Obviously, due to their different metallicity, the massive stars in the LMC and the SMC follow different evolutionary paths. Their winds differ significantly, and the key feedback agents are different. As a consequence, the star formation can proceed in different modes.