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Restful choreographies
(2019)
Business process management has become a key instrument to organize work as many companies represent their operations in business process models. Recently, business process choreography diagrams have been introduced as part of the Business Process Model and Notation standard to represent interactions between business processes, run by different partners. When it comes to the interactions between services on the Web, Representational State Transfer (REST) is one of the primary architectural styles employed by web services today. Ideally, the RESTful interactions between participants should implement the interactions defined at the business choreography level.
The problem, however, is the conceptual gap between the business process choreography diagrams and RESTful interactions. Choreography diagrams, on the one hand, are modeled from business domain experts with the purpose of capturing, communicating and, ideally, driving the business interactions. RESTful interactions, on the other hand, depend on RESTful interfaces that are designed by web engineers with the purpose of facilitating the interaction between participants on the internet. In most cases however, business domain experts are unaware of the technology behind web service interfaces and web engineers tend to overlook the overall business goals of web services. While there is considerable work on using process models during process implementation, there is little work on using choreography models to implement interactions between business processes. This thesis addresses this research gap by raising the following research question: How to close the conceptual gap between business process choreographies and RESTful interactions? This thesis offers several research contributions that jointly answer the research question.
The main research contribution is the design of a language that captures RESTful interactions between participants---RESTful choreography modeling language. Formal completeness properties (with respect to REST) are introduced to validate its instances, called RESTful choreographies. A systematic semi-automatic method for deriving RESTful choreographies from business process choreographies is proposed. The method employs natural language processing techniques to translate business interactions into RESTful interactions. The effectiveness of the approach is shown by developing a prototypical tool that evaluates the derivation method over a large number of choreography models.
In addition, the thesis proposes solutions towards implementing RESTful choreographies. In particular, two RESTful service specifications are introduced for aiding, respectively, the execution of choreographies' exclusive gateways and the guidance of RESTful interactions.
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.
One method of embedding groups into skew fields was introduced by A. I. Mal'tsev and B. H. Neumann (cf. [18, 19]). If G is an ordered group and F is a skew field, the set F((G)) of formal power series over F in G with well-ordered support forms a skew field into which the group ring F[G] can be embedded. Unfortunately it is not suficient that G is left-ordered since F((G)) is only an F-vector space in this case as there is no natural way to define a multiplication on F((G)). One way to extend the original idea onto left-ordered groups is to examine the endomorphism ring of F((G)) as explored by N. I. Dubrovin (cf. [5, 6]). It is possible to embed any crossed product ring F[G; η, σ] into the endomorphism ring of F((G)) such that each non-zero element of F[G; η, σ] defines an automorphism of F((G)) (cf. [5, 10]). Thus, the rational closure of F[G; η, σ] in the endomorphism ring of F((G)), which we will call the Dubrovin-ring of F[G; η, σ], is a potential candidate for a skew field of fractions of F[G; η, σ]. The methods of N. I. Dubrovin allowed to show that specific classes of groups can be embedded into a skew field. For example, N. I. Dubrovin contrived some special criteria, which are applicable on the universal covering group of SL(2, R). These methods have also been explored by J. Gräter and R. P. Sperner (cf. [10]) as well as N.H. Halimi and T. Ito (cf. [11]). Furthermore, it is of interest to know if skew fields of fractions are unique. For example, left and right Ore domains have unique skew fields of fractions (cf. [2]). This is not the general case as for example the free group with 2 generators can be embedded into non-isomorphic skew fields of fractions (cf. [12]). It seems likely that Ore domains are the most general case for which unique skew fields of fractions exist. One approach to gain uniqueness is to restrict the search to skew fields of fractions with additional properties. I. Hughes has defined skew fields of fractions of crossed product rings F[G; η, σ] with locally indicable G which fulfill a special condition. These are called Hughes-free skew fields of fractions and I. Hughes has proven that they are unique if they exist [13, 14]. This thesis will connect the ideas of N. I. Dubrovin and I. Hughes. The first chapter contains the basic terminology and concepts used in this thesis. We present methods provided by N. I. Dubrovin such as the complexity of elements in rational closures and special properties of endomorphisms of the vector space of formal power series F((G)). To combine the ideas of N.I. Dubrovin and I. Hughes we introduce Conradian left-ordered groups of maximal rank and examine their connection to locally indicable groups. Furthermore we provide notations for crossed product rings, skew fields of fractions as well as Dubrovin-rings and prove some technical statements which are used in later parts. The second chapter focuses on Hughes-free skew fields of fractions and their connection to Dubrovin-rings. For that purpose we introduce series representations to interpret elements of Hughes-free skew fields of fractions as skew formal Laurent series. This 1 Introduction allows us to prove that for Conradian left-ordered groups G of maximal rank the statement "F[G; η, σ] has a Hughes-free skew field of fractions" implies "The Dubrovin ring of F [G; η, σ] is a skew field". We will also prove the reverse and apply the results to give a new prove of Theorem 1 in [13]. Furthermore we will show how to extend injective ring homomorphisms of some crossed product rings onto their Hughes-free skew fields of fractions. At last we will be able to answer the open question whether Hughes--free skew fields are strongly Hughes-free (cf. [17, page 53]).
Introduction: Cystic fibrosis (CF) is a genetic disease which disrupts the function of an epithelial surface anion channel, CFTR (cystic fibrosis transmembrane conductance regulator). Impairment to this channel leads to inflammation and infection in the lung causing the majority of morbidity and mortality. However, CF is a multiorgan disease affecting many tissues, including vascular smooth muscle. Studies have revealed young people with cystic fibrosis lacking inflammation and infection still demonstrate vascular endothelial dysfunction, measured per flow-mediated dilation (FMD). In other disease cohorts, i.e. diabetic and obese, endurance exercise interventions have been shown improve or taper this impairment. However, long-term exercise interventions are risky, as well as costly in terms of time and resources. Nevertheless, emerging research has correlated the acute effects of exercise with its long-term benefits and advocates the study of acute exercise effects on FMD prior to longitudinal studies. The acute effects of exercise on FMD have previously not been examined in young people with CF, but could yield insights on the potential benefits of long-term exercise interventions.
The aims of these studies were to 1) develop and test the reliability of the FMD method and its applicability to study acute exercise effects; 2) compare baseline FMD and the acute exercise effect on FMD between young people with and without CF; and 3) explore associations between the acute effects of exercise on FMD and demographic characteristics, physical activity levels, lung function, maximal exercise capacity or inflammatory hsCRP levels.
Methods: Thirty young volunteers (10 people with CF, 10 non-CF and 10 non-CF active matched controls) between the ages of 10 and 30 years old completed blood draws, pulmonary function tests, maximal exercise capacity tests and baseline FMD measurements, before returning approximately 1 week later and performing a 30-min constant load training at 75% HRmax. FMD measurements were taken prior, immediately after, 30 minutes after and 1 hour after constant load training. ANOVAs and repeated measures ANOVAs were employed to explore differences between groups and timepoints, respectively. Linear regression was implemented and evaluated to assess correlations between FMD and demographic characteristics, physical activity levels, lung function, maximal exercise capacity or inflammatory hsCRP levels. For all comparisons, statistical significance was set at a p-value of α < 0.05.
Results: Young people with CF presented with decreased lung function and maximal exercise capacity compared to matched controls. Baseline FMD was also significantly decreased in the CF group (CF: 5.23% v non-CF: 8.27% v non-CF active: 9.12%). Immediately post-training, FMD was significantly attenuated (approximately 40%) in all groups with CF still demonstrating the most minimal FMD. Follow-up measurements of FMD revealed a slow recovery towards baseline values 30 min post-training and improvements in the CF and non-CF active groups 60 min post-training. Linear regression exposed significant correlations between maximal exercise capacity (VO2 peak), BMI and FMD immediately post-training.
Conclusion: These new findings confirm that CF vascular endothelial dysfunction can be acutely modified by exercise and will aid in underlining the importance of exercise in CF populations. The potential benefits of long-term exercise interventions on vascular endothelial dysfunction in young people with CF warrants further investigation.
In den letzten Jahrzehnten fand auch in der Beschichtungsindustrie ein Umdenken hin zu umweltfreundlicheren Farben und Lacken statt. Allerdings basieren auch neue Lösungen meist nicht auf Biopolymeren und in einem noch geringeren Anteil auf wasserbasierten Beschichtungssystemen aus nachwachsenden Rohstoffen. Dies stellt den Anknüpfungspunkt dieser Arbeit dar, in der untersucht wurde, ob das Biopolymer Stärke das Potenzial zum wasserbasierten Filmbildner für Farben und Lacke besitzt. Dabei müssen angelehnt an etablierte synthetische Marktprodukte die folgenden Kriterien erfüllt werden: Die wässrige Dispersion muss mindestens einen 30%igen Feststoffgehalt haben, bei Raumtemperatur verarbeitet werden können und Viskositäten zwischen 10^2-10^3 mPa·s aufweisen. Die finale Beschichtung muss einen geschlossenen Film bilden und sehr gute Haftfestigkeiten zu einer spezifischen Oberfläche, in dieser Arbeit Glas, besitzen. Als Grundlage für die Modifizierung der Stärke wurde eine Kombination von molekularem Abbau und chemischer Funktionalisierung ausgewählt. Da nicht bekannt war, welchen Einfluss die Stärkeart, die gewählte Abbaureaktion als auch verschiedene Substituenten auf die Dispersionsherstellung und deren Eigenschaften sowie die Beschichtungseigenschaften ausüben könnten, wurden die strukturellen Parameter getrennt voneinander untersucht.
Das erste Themengebiet beinhaltete den oxidativen Abbau von Kartoffel- und Palerbsenstärke mittels des Hypochlorit-Abbaus (OCl-) und des ManOx-Abbaus (H2O2, KMnO4). Mit beiden Abbaureaktionen konnten vergleichbare gewichtsmittlere Molmassen (Mw) von 2·10^5-10^6 g/mol (GPC-MALS) hergestellt werden. Allerdings führten die gewählten Reaktionsbedingungen beim ManOx-Abbau zur Bildung von Gelpartikeln. Diese lagen im µm-Bereich (DLS und Kryo-REM-Messungen) und hatten zur Folge, dass die ManOx-Proben deutlich erhöhte Viskositäten (c: 7,5 %; 9-260 mPa·s) im Vergleich zu den OCl--Proben (4-10 mPa·s) bei scherverdünnendem Verhalten besaßen und die Eigenschaften von viskoelastischen Gelen (G‘ > G‘‘) zeigten. Des Weiteren wiesen sie reduzierte Heißwasserlöslichkeiten (95 °C, vorrangig: 70-99 %) auf. Der OCl--Abbau führte zu hydrophileren (Carboxylgruppengehalt bis zu 6,1 %; ManOx: bis zu 3,1 %), nach 95 °C-Behandlung vollständig wasserlöslichen abgebauten Stärken, die ein Newtonsches Fließverhalten mit Eigenschaften einer viskoelastischen Flüssigkeit (G‘‘ > G‘) hatten. Die OCl--Proben konnten im Vergleich zu den ManOx-Produkten (10-20 %) zu konzentrierteren Dispersionen (20-40 %) verarbeitet werden, die gleichzeitig die Einschränkung von anwendungsrelevanten Mw auf < 7·10^5 g/mol zuließen (Konzentration sollte > 30 % sein). Außerdem führten nur die OCl--Proben der Kartoffelstärke zu transparenten (alle anderen waren opak) geschlossenen Beschichtungsfilmen. Somit hebt sich die Kombination von OCl--Abbau und Kartoffelstärke mit Hinblick auf die Endanwendung ab.
Das zweite Themengebiet umfasste Untersuchungen zum Einfluss von Ester- und Hydroxyalkylether-Substituenten auf Basis einer industriell abgebauten Kartoffelstärke (Mw: 1,2·10^5 g/mol) vor allem auf die Dispersionsherstellung, die rheologischen Eigenschaften der Dispersionen und die Beschichtungseigenschaften in Kombination mit Glassubstraten. Dazu wurden Ester und Ether mit DS/MS-Werten von 0,07-0,91 synthetisiert. Die Derivate konnten zu wasserbasierten Dispersionen mit Konzentrationen von 30-45 % verarbeitet werden, wobei bei hydrophoberen Modifikaten ein Co-Lösemittel, Diethylenglycolmonobutylether (DEGBE), eingesetzt werden musste. Die Feststoffgehalte sanken dabei für beide Derivatklassen vor allem mit zunehmender Alkylkettenlänge. Die anwendungsrelevanten Viskositäten (323-1240 mPa·s) stiegen auf Grund von Wechselwirkungen tendenziell mit DS/MS und Alkylkettenlänge an. Hinsichtlich der Beschichtungseigenschaften erwiesen sich die Ester vergleichend zu den Ethern als die bevorzugte Substituentenklasse, da nur die Ester geschlossene, defektfreie und mehrheitlich transparente Beschichtungsfilme bildeten, die exzellente bis sehr gute Haftfestigkeiten (ISO Klasse: 0 und 1) auf Glas besaßen. Die Ether bildeten mehrheitlich brüchige Filme. Basierend auf der Kombination der Ergebnisse aus Lösemittelaustausch, den rheologischen Untersuchungen und zusätzlichen Oberflächenspannungsmessungen (30-61 mN/m) konnte geschlossen werden, dass wahrscheinlich fehlende oder schlechte Haftfestigkeiten vorrangig akkumuliertem Wasser in den Beschichtungsfilmen (visuell: trüb oder weiß) geschuldet sind, während die Brüchigkeit vermutlich auf Wechselwirkungen (H-Brücken Wechselwirkungen, hydrophobe Wechselwirkungen) zwischen den Polymeren zurückgeführt werden kann.
Insgesamt scheint die Kombination aus Kartoffelstärke basierend auf dem OCl--Abbau mit Mw < 7·10^5 g/mol und einem Estersubstituenten eine gute Wahl für wasserbasierte Dispersionen mit hohen Feststoffkonzentrationen (> 30 %), guter Filmbildung und exzellenten Haftungen auf Glas zu sein.
A contemporary challenge in Ecology and Evolutionary Biology is to anticipate the fate of populations of organisms in the context of a changing world. Climate change and landscape changes due to anthropic activities have been of major concern in the contemporary history. Organisms facing these threats are expected to respond by local adaptation (i.e., genetic changes or phenotypic plasticity) or by shifting their distributional range (migration). However, there are limits to their responses. For example, isolated populations will have more difficulties in developing adaptive innovations by means of genetic changes than interconnected metapopulations. Similarly, the topography of the environment can limit dispersal opportunities for crawling organisms as compared to those that rely on wind. Thus, populations of species with different life history strategy may differ in their ability to cope with changing environmental conditions. However, depending on the taxon, empirical studies investigating organisms’ responses to environmental change may become too complex, long and expensive; plus, complications arising from dealing with endangered species. In consequence, eco-evolutionary modeling offers an opportunity to overcome these limitations and complement empirical studies, understand the action and limitations of underlying mechanisms, and project into possible future scenarios. In this work I take a modeling approach and investigate the effect and relative importance of evolutionary mechanisms (including phenotypic plasticity) on the ability for local adaptation of populations with different life strategy experiencing climate change scenarios. For this, I performed a review on the state of the art of eco-evolutionary Individual-Based Models (IBMs) and identify gaps for future research. Then, I used the results from the review to develop an eco-evolutionary individual-based modeling tool to study the role of genetic and plastic mechanisms in promoting local adaption of populations of organisms with different life strategies experiencing scenarios of climate change and environmental stochasticity. The environment was simulated through a climate variable (e.g., temperature) defining a phenotypic optimum moving at a given rate of change. The rate of change was changed to simulate different scenarios of climate change (no change, slow, medium, rapid climate change). Several scenarios of stochastic noise color resembling different climatic conditions were explored. Results show that populations of sexual species will rely mainly on standing genetic variation and phenotypic plasticity for local adaptation. Population of species with relatively slow growth rate (e.g., large mammals) – especially those of small size – are the most vulnerable, particularly if their plasticity is limited (i.e., specialist species). In addition, whenever organisms from these populations are capable of adaptive plasticity, they can buffer fitness losses in reddish climatic conditions. Likewise, whenever they can adjust their plastic response (e.g., bed-hedging strategy) they will cope with bluish environmental conditions as well. In contrast, life strategies of high fecundity can rely on non-adaptive plasticity for their local adaptation to novel environmental conditions, unless the rate of change is too rapid. A recommended management measure is to guarantee interconnection of isolated populations into metapopulations, such that the supply of useful genetic variation can be increased, and, at the same time, provide them with movement opportunities to follow their preferred niche, when local adaptation becomes problematic. This is particularly important for bluish and reddish climatic conditions, when the rate of change is slow, or for any climatic condition when the level of stress (rate of change) is relatively high.
A central insight from psychological studies on human eye movements is that eye movement patterns are highly individually characteristic. They can, therefore, be used as a biometric feature, that is, subjects can be identified based on their eye movements. This thesis introduces new machine learning methods to identify subjects based on their eye movements while viewing arbitrary content. The thesis focuses on probabilistic modeling of the problem, which has yielded the best results in the most recent literature. The thesis studies the problem in three phases by proposing a purely probabilistic, probabilistic deep learning, and probabilistic deep metric learning approach. In the first phase, the thesis studies models that rely on psychological concepts about eye movements. Recent literature illustrates that individual-specific distributions of gaze patterns can be used to accurately identify individuals. In these studies, models were based on a simple parametric family of distributions. Such simple parametric models can be robustly estimated from sparse data, but have limited flexibility to capture the differences between individuals. Therefore, this thesis proposes a semiparametric model of gaze patterns that is flexible yet robust for individual identification. These patterns can be understood as domain knowledge derived from psychological literature. Fixations and saccades are examples of simple gaze patterns. The proposed semiparametric densities are drawn under a Gaussian process prior centered at a simple parametric distribution. Thus, the model will stay close to the parametric class of densities if little data is available, but it can also deviate from this class if enough data is available, increasing the flexibility of the model. The proposed method is evaluated on a large-scale dataset, showing significant improvements over the state-of-the-art. Later, the thesis replaces the model based on gaze patterns derived from psychological concepts with a deep neural network that can learn more informative and complex patterns from raw eye movement data. As previous work has shown that the distribution of these patterns across a sequence is informative, a novel statistical aggregation layer called the quantile layer is introduced. It explicitly fits the distribution of deep patterns learned directly from the raw eye movement data. The proposed deep learning approach is end-to-end learnable, such that the deep model learns to extract informative, short local patterns while the quantile layer learns to approximate the distributions of these patterns. Quantile layers are a generic approach that can converge to standard pooling layers or have a more detailed description of the features being pooled, depending on the problem. The proposed model is evaluated in a large-scale study using the eye movements of subjects viewing arbitrary visual input. The model improves upon the standard pooling layers and other statistical aggregation layers proposed in the literature. It also improves upon the state-of-the-art eye movement biometrics by a wide margin. Finally, for the model to identify any subject — not just the set of subjects it is trained on — a metric learning approach is developed. Metric learning learns a distance function over instances. The metric learning model maps the instances into a metric space, where sequences of the same individual are close, and sequences of different individuals are further apart. This thesis introduces a deep metric learning approach with distributional embeddings. The approach represents sequences as a set of continuous distributions in a metric space; to achieve this, a new loss function based on Wasserstein distances is introduced. The proposed method is evaluated on multiple domains besides eye movement biometrics. This approach outperforms the state of the art in deep metric learning in several domains while also outperforming the state of the art in eye movement biometrics.
Phytoplankton growth depends not only on the mean intensity but also on the dynamics of the light supply. The nonlinear light-dependency of growth is characterized by a small number of basic parameters: the compensation light intensity PARcompμ, where production and losses are balanced, the growth efficiency at sub-saturating light αµ, and the maximum growth rate at saturating light µmax. In surface mixed layers, phytoplankton may rapidly move between high light intensities and almost darkness. Because of the different frequency distribution of light and/or acclimation processes, the light-dependency of growth may differ between constant and fluctuating light. Very few studies measured growth under fluctuating light at a sufficient number of mean light intensities to estimate the parameters of the growth-irradiance relationship. Hence, the influence of light dynamics on µmax, αµ and PARcompμ are still largely unknown. By extension, accurate modelling predictions of phytoplankton development under fluctuating light exposure remain difficult to make. This PhD thesis does not intend to directly extrapolate few experimental results to aquatic systems – but rather improving the mechanistic understanding of the variation of the light-dependency of growth under light fluctuations and effects on phytoplankton development.
In Lake TaiHu and at the Three Gorges Reservoir (China), we incubated phytoplankton communities in bottles placed either at fixed depths or moved vertically through the water column to mimic vertical mixing. Phytoplankton at fixed depths received only the diurnal changes in light (defined as constant light regime), while phytoplankton received rapidly fluctuating light by superimposing the vertical light gradient on the natural sinusoidal diurnal sunlight. The vertically moved samples followed a circular movement with 20 min per revolution, replicating to some extent the full overturn of typical Langmuir cells. Growth, photosynthesis, oxygen production and respiration of communities (at Lake TaiHu) were
measured. To complete these investigations, a physiological experiment was performed in the laboratory on a toxic strain of Microcystis aeruginosa (FACBH 1322) incubated under 20 min period fluctuating light. Here, we measured electron transport rates and net oxygen production at a much higher time resolution (single minute timescale).
The present PhD thesis provides evidence for substantial effects of fluctuating light on the eco-physiology of phytoplankton. Both experiments performed under semi-natural conditions in Lake TaiHu and at the Three Gorges Reservoir gave similar results. The significant decline in community growth efficiencies αµ under fluctuating light was caused for a great share by different frequency distribution of light intensities that shortened the effective daylength for production. The remaining gap in community αµ was attributed to species-specific photoacclimation mechanisms and to light-dependent respiratory losses. In contrast, community maximal growth rates µmax were similar between incubations at constant and fluctuating light. At daily growth saturating light supply, differences in losses for biosynthesis between the two light regimes were observed. Phytoplankton experiencing constant light suffered photo-inhibition - leading to photosynthesis foregone and additional respiratory costs for photosystems repair. On the contrary, intermittent exposure to low and high light intensities prevented photo-inhibition of mixed algae but forced them to develop alternative light strategy. They better harvested and exploited surface irradiance by enhancing their photosynthesis. In the laboratory, we showed that Microcystis aeruginosa increased its oxygen consumption by dark respiration in the light few minutes only after exposure to increasing light intensities. More, we proved that within a simulated Langmuir cell, the net production at saturating light and the compensation light intensity for production at limiting light are positively related. These results are best explained by an accumulation of photosynthetic products at increasing irradiance and mobilization of these fresh resources by rapid enhancement of dark respiration for maintenance and biosynthesis at decreasing irradiance. At the daily timescale, we showed that the enhancement of photosynthesis at high irradiance for biosynthesis of species increased their maintenance respiratory costs at limiting light. Species-specific growth at saturating light µmax and compensation light intensity for growth PARcompμ of species incubated in Lake TaiHu were positively related. Because of this species-specific physiological tradeoff, species displayed different light affinities to limiting and saturating light - thereby exhibiting a gleaner-opportunist tradeoff. In Lake TaiHu, we showed that inter-specific differences in light acquisition traits (µmax and PARcompμ) allowed coexis¬tence of species on a gradient of constant
light while avoiding competitive exclusion. More interestingly we demonstrated for the first time that vertical mixing (inducing fluctuating light supply for phytoplankton) may alter or even reverse the light utilization strategies of species within couple of days. The intra-specific variation in traits under fluctuating light increased the niche space for acclimated species, precluding competitive exclusion.
Overall, this PhD thesis contributes to a better understanding of phytoplankton eco-physiology under fluctuating light supply. This work could enhance the quality of predictions of phytoplankton development under certain weather conditions or climate change scenarios.
Hepcidin-25 (Hep-25) plays a crucial role in the control of iron homeostasis. Since the dysfunction of the hepcidin pathway leads to multiple diseases as a result of iron imbalance, hepcidin represents a potential target for the diagnosis and treatment of disorders of iron metabolism. Despite intense research in the last decade targeted at developing a selective immunoassay for iron disorder diagnosis and treatment and better understanding the ferroportin-hepcidin interaction, questions remain. The key to resolving these underlying questions is acquiring exact knowledge of the 3D structure of native Hep-25. Since it was determined that the N-terminus, which is responsible for the bioactivity of Hep-25, contains a small Cu(II)-binding site known as the ATCUN motif, it was assumed that the Hep-25-Cu(II) complex is the native, bioactive form of the hepcidin. This structure has thus far not been elucidated in detail. Owing to the lack of structural information on metal-bound Hep-25, little is known about its possible biological role in iron metabolism. Therefore, this work is focused on structurally characterizing the metal-bound Hep-25 by NMR spectroscopy and molecular dynamics simulations. For the present work, a protocol was developed to prepare and purify properly folded Hep-25 in high quantities. In order to overcome the low solubility of Hep-25 at neutral pH, we introduced the C-terminal DEDEDE solubility tag. The metal binding was investigated through a series of NMR spectroscopic experiments to identify the most affected amino acids that mediate metal coordination. Based on the obtained NMR data, a structural calculation was performed in order to generate a model structure of the Hep-25-Ni(II) complex. The DEDEDE tag was excluded from the structural calculation due to a lack of NMR restraints. The dynamic nature and fast exchange of some of the amide protons with solvent reduced the overall number of NMR restraints needed for a high-quality structure. The NMR data revealed that the 20 Cterminal Hep-25 amino acids experienced no significant conformational changes, compared to published results, as a result of a pH change from pH 3 to pH 7 and metal binding. A 3D model of the Hep-25-Ni(II) complex was constructed from NMR data recorded for the hexapeptideNi(II) complex and Hep-25-DEDEDE-Ni(II) complex in combination with the fixed conformation of 19 C-terminal amino acids. The NMR data of the Hep-25-DEDEDE-Ni(II) complex indicates that the ATCUN motif moves independently from the rest of the structure. The 3D model structure of the metal-bound Hep-25 allows for future works to elucidate hepcidin’s interaction with its receptor ferroportin and should serve as a starting point for the development of antibodies with improved selectivity.
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.
Increasing concerns regarding the environmental impact of our chemical production have shifted attention towards possibilities for sustainable biotechnology. One-carbon (C1) compounds, including methane, methanol, formate and CO, are promising feedstocks for future bioindustry. CO2 is another interesting feedstock, as it can also be transformed using renewable energy to other C1 feedstocks for use. While formaldehyde is not suitable as a feedstock due to its high toxicity, it is a central intermediate in the process of C1 assimilation. This thesis explores formaldehyde metabolism and aims to engineer formaldehyde assimilation in the model organism Escherichia coli for the future C1-based bioindustry.
The first chapter of the thesis aims to establish growth of E. coli on formaldehyde via the most efficient naturally occurring route, the ribulose monophosphate pathway. Linear variants of the pathway were constructed in multiple-gene knockouts strains, coupling E. coli growth to the activities of the key enzymes of the pathway. Formaldehyde-dependent growth was achieved in rationally designed strains. In the final strain, the synthetic pathway provides the cell with almost all biomass and energy requirements.
In the second chapter, taking advantage of the unique feature of its reactivity, formaldehyde assimilation via condensation with glycine and pyruvate by two promiscuous aldolases was explored. Facilitated by these two reactions, the newly designed homoserine cycle is expected to support higher yields of a wide array of products than its counterparts. By dividing the pathway into segments and coupling them to the growth of dedicated strains, all pathway reactions were demonstrated to be sufficiently active. The work paves a way for future implementation of a highly efficient route for C1 feedstocks into commodity chemicals.
In the third chapter, the in vivo rate of the spontaneous formaldehyde tetrahydrofolate condensation to methylene-tetrahydrofolate was assessed in order to evaluate its applicability as a biotechnological process. Tested within an E. coli strain deleted in essential genes for native methylene-tetrahydrofolate biosynthesis, the reaction was shown to support the production of this essential intermediate. However, only low growth rates were observed and only at high formaldehyde concentrations. Computational analysis dependent on in vivo evidence from this strain deduced the slow rate of this spontaneous reaction, thus ruling out its substantial contribution to growth on C1 feedstocks.
The reactivity of formaldehyde makes it highly toxic. In the last chapter, the formation of thioproline, the condensation product of cysteine and formaldehyde, was confirmed to contribute this toxicity effect. Xaa-Pro aminopeptidase (PepP), which genetically links with folate metabolism, was shown to hydrolyze thioproline-containing peptides. Deleting pepP increased strain sensitivity to formaldehyde, pointing towards the toxicity of thioproline-containing peptides and the importance of their removal. The characterization in this study could be useful in handling this toxic intermediate.
Overall, this thesis identified challenges related to formaldehyde metabolism and provided novel solutions towards a future bioindustry based on sustainable C1 feedstocks in which formaldehyde serves as a key intermediate.
Accurate weather observations are the keystone to many quantitative applications, such as precipitation monitoring and nowcasting, hydrological modelling and forecasting, climate studies, as well as understanding precipitation-driven natural hazards (i.e. floods, landslides, debris flow). Weather radars have been an increasingly popular tool since the 1940s to provide high spatial and temporal resolution precipitation data at the mesoscale, bridging the gap between synoptic and point scale observations. Yet, many institutions still struggle to tap the potential of the large archives of reflectivity, as there is still much to understand about factors that contribute to measurement errors, one of which is calibration. Calibration represents a substantial source of uncertainty in quantitative precipitation estimation (QPE). A miscalibration of a few dBZ can easily deteriorate the accuracy of precipitation estimates by an order of magnitude. Instances where rain cells carrying torrential rains are misidentified by the radar as moderate rain could mean the difference between a timely warning and a devastating flood.
Since 2012, the Philippine Atmospheric, Geophysical, and Astronomical Services Administration (PAGASA) has been expanding the country’s ground radar network. We had a first look into the dataset from one of the longest running radars (the Subic radar) after devastating week-long torrential rains and thunderstorms in August 2012 caused by the annual southwestmonsoon and enhanced by the north-passing Typhoon Haikui. The analysis of the rainfall spatial distribution revealed the added value of radar-based QPE in comparison to interpolated rain gauge observations. However, when compared with local gauge measurements, severe miscalibration of the Subic radar was found. As a consequence, the radar-based QPE would have underestimated the rainfall amount by up to 60% if they had not been adjusted by rain gauge observations—a technique that is not only affected by other uncertainties, but which is also not feasible in other regions of the country with very sparse rain gauge coverage.
Relative calibration techniques, or the assessment of bias from the reflectivity of two radars, has been steadily gaining popularity. Previous studies have demonstrated that reflectivity observations from the Tropical Rainfall Measuring Mission (TRMM) and its successor, the Global Precipitation Measurement (GPM), are accurate enough to serve as a calibration reference for ground radars over low-to-mid-latitudes (± 35 deg for TRMM; ± 65 deg for GPM). Comparing spaceborne radars (SR) and ground radars (GR) requires cautious consideration of differences in measurement geometry and instrument specifications, as well as temporal coincidence. For this purpose, we implement a 3-D volume matching method developed by Schwaller and Morris (2011) and extended by Warren et al. (2018) to 5 years worth of observations from the Subic radar. In this method, only the volumetric intersections of the SR and GR beams are considered.
Calibration bias affects reflectivity observations homogeneously across the entire radar domain. Yet, other sources of systematic measurement errors are highly heterogeneous in space, and can either enhance or balance the bias introduced by miscalibration. In order to account for such heterogeneous errors, and thus isolate the calibration bias, we assign a quality index to each matching SR–GR volume, and thus compute the GR calibration bias as a qualityweighted average of reflectivity differences in any sample of matching SR–GR volumes. We exemplify the idea of quality-weighted averaging by using beam blockage fraction (BBF) as a quality variable. Quality-weighted averaging is able to increase the consistency of SR and GR observations by decreasing the standard deviation of the SR–GR differences, and thus increasing the precision of the bias estimates.
To extend this framework further, the SR–GR quality-weighted bias estimation is applied to the neighboring Tagaytay radar, but this time focusing on path-integrated attenuation (PIA) as the source of uncertainty. Tagaytay is a C-band radar operating at a lower wavelength and is therefore more affected by attenuation. Applying the same method used for the Subic radar, a time series of calibration bias is also established for the Tagaytay radar.
Tagaytay radar sits at a higher altitude than the Subic radar and is surrounded by a gentler terrain, so beam blockage is negligible, especially in the overlapping region. Conversely, Subic radar is largely affected by beam blockage in the overlapping region, but being an SBand radar, attenuation is considered negligible. This coincidentally independent uncertainty contributions of each radar in the region of overlap provides an ideal environment to experiment with the different scenarios of quality filtering when comparing reflectivities from the two ground radars. The standard deviation of the GR–GR differences already decreases if we consider either BBF or PIA to compute the quality index and thus the weights. However, combining them multiplicatively resulted in the largest decrease in standard deviation, suggesting that taking both factors into account increases the consistency between the matched samples.
The overlap between the two radars and the instances of the SR passing over the two radars at the same time allows for verification of the SR–GR quality-weighted bias estimation method. In this regard, the consistency between the two ground radars is analyzed before and after bias correction is applied. For cases when all three radars are coincident during a significant rainfall event, the correction of GR reflectivities with calibration bias estimates from SR overpasses dramatically improves the consistency between the two ground radars which have shown incoherent observations before correction. We also show that for cases where adequate SR coverage is unavailable, interpolating the calibration biases using a moving average can be used to correct the GR observations for any point in time to some extent. By using the interpolated biases to correct GR observations, we demonstrate that bias correction reduces the absolute value of the mean difference in most cases, and therefore improves the consistency between the two ground radars.
This thesis demonstrates that in general, taking into account systematic sources of uncertainty that are heterogeneous in space (e.g. BBF) and time (e.g. PIA) allows for a more consistent estimation of calibration bias, a homogeneous quantity. The bias still exhibits an unexpected variability in time, which hints that there are still other sources of errors that remain unexplored. Nevertheless, the increase in consistency between SR and GR as well as between the two ground radars, suggests that considering BBF and PIA in a weighted-averaging approach is a step in the right direction.
Despite the ample room for improvement, the approach that combines volume matching between radars (either SR–GR or GR–GR) and quality-weighted comparison is readily available for application or further scrutiny. As a step towards reproducibility and transparency in atmospheric science, the 3D matching procedure and the analysis workflows as well as sample data are made available in public repositories. Open-source software such as Python and wradlib are used for all radar data processing in this thesis. This approach towards open science provides both research institutions and weather services with a valuable tool that can be applied to radar calibration, from monitoring to a posteriori correction of archived data.
Business process management (BPM) deals with modeling, executing, monitoring, analyzing, and improving business processes. During execution, the process communicates with its environment to get relevant contextual information represented as events. Recent development of big data and the Internet of Things (IoT) enables sources like smart devices and sensors to generate tons of events which can be filtered, grouped, and composed to trigger and drive business processes.
The industry standard Business Process Model and Notation (BPMN) provides several event constructs to capture the interaction possibilities between a process and its environment, e.g., to instantiate a process, to abort an ongoing activity in an exceptional situation, to take decisions based on the information carried by the events, as well as to choose among the alternative paths for further process execution. The specifications of such interactions are termed as event handling. However, in a distributed setup, the event sources are most often unaware of the status of process execution and therefore, an event is produced irrespective of the process being ready to consume it. BPMN semantics does not support such scenarios and thus increases the chance of processes getting delayed or getting in a deadlock by missing out on event occurrences which might still be relevant.
The work in this thesis reviews the challenges and shortcomings of integrating real-world events into business processes, especially the subscription management. The basic integration is achieved with an architecture consisting of a process modeler, a process engine, and an event processing platform. Further, points of subscription and unsubscription along the process execution timeline are defined for different BPMN event constructs. Semantic and temporal dependencies among event subscription, event occurrence, event consumption and event unsubscription are considered. To this end, an event buffer with policies for updating the buffer, retrieving the most suitable event for the current process instance, and reusing the event has been discussed that supports issuing of early subscription.
The Petri net mapping of the event handling model provides our approach with a translation of semantics from a business process perspective. Two applications based on this formal foundation are presented to support the significance of different event handling configurations on correct process execution and reachability of a process path. Prototype implementations of the approaches show that realizing flexible event handling is feasible with minor extensions of off-the-shelf process engines and event platforms.
Bildungsort Familie
(2019)
In der Bildungs- und Familienforschung wird die intergenerationale Weitergabe von Bildung innerhalb der Familie hauptsächlich unter dem Blickwinkel des schulischen Erfolges der nachwachsenden Generation thematisiert. „Wie“ aber bildungsbezogene Transferprozesse innerhalb der Familie konkret ablaufen, bleibt jedoch in der deutschen Forschungslandschaft weitestgehend unbearbeitet. An dieser Stelle setzt diese qualitativ angelegte Arbeit an. Ziel dieser Arbeit ist, bildungsbezogene Transferprozesse innerhalb von russischen Dreigenerationenfamilien, die aus der ehemaligen Sowjetunion nach Berlin seit 1989 ausgewandert sind und zwischen der Großeltern-, Elterngeneration und der Enkelgeneration ablaufen, zu untersuchen. Hinter diesen Transferprozessen verbergen sich im Sinne Bourdieus bewusste und unbewusste Bildungsstrategien der interviewten Familienmitglieder. Im Rahmen dieser Arbeit wurden zwei Spätaussiedlerfamilien – zu diesen zählen Familie Hoffmann und Familie Popow, sowie zwei russisch-jüdische Familien – zu diesen zählen Familie Rosenthal und Familie Buchbinder, interviewt. Es wurden mit den einzelnen Mitgliedern der vier untersuchten Dreigenerationenfamilien Gruppendiskussionen sowie mit je einem Vertreter einer Generation leitfadengestützte Einzelinterviews geführt. Die Erhebungsphase fand in Berlin im Zeitraum von 2010 bis 2012 statt. Das auf diese Weise gewonnene empirische Material wurde mithilfe der dokumentarischen Methode nach Bohnsack ausgewertet. Hierdurch wurde es möglich die implizite Selbstverständlichkeit, mit der sich Bildung in Familien nach Bourdieu habituell vollzieht, einzufangen und rekonstruierbar zu machen. In der Arbeit wurden eine habitustheoretische Interpretation der russischen Dreigenerationenfamilien und die entsprechende Feldanalyse nach Bourdieu vorgenommen. In diesem Zusammenhang wurde der soziale Raum der untersuchten Familien in der Ankunftsgesellschaft bezüglich ihres Vergleichshorizontes der Herkunftsgesellschaft rekonstruiert. Weiter wurde der Bildungstransfer vor dem jeweiligen Erlebnishintergrund der einzelnen Familien untersucht und diesbezüglich eine Typisierung vorgenommen.
Im Rahmen dieser Untersuchung konnten neue Erkenntnisse zum bisher unerforschten Feld des Bildungstransfers russischer Dreigenerationenfamilien in Berlin gewonnen werden. Ein wesentliches Ergebnis dieser Arbeit ist, dass die Anwendung von Bourdieus Klassentheorie auch auf Gruppen, die in einer sozialistischen Gesellschaft sozialisiert wurden und in eine kapitalistisch orientierte Gesellschaft ausgewandert sind, produktiv sein kann. Ein weiteres zentrales Ergebnis der Studie ist, dass bei zwei der vier untersuchten Familien die Migration den intergenerationalen Bildungstransfer beeinflusste. In diesem Zusammenhang weist Familie Rosenthal durch die Migration einen „gespaltenen“ Habitus auf. Dieser ist darauf zurückzuführen, dass diese Familie bei der Planung des Berufes für die Enkelin in Berlin sich am Praktischen und Notwendigen orientierte. Während die bewusste Bildungsstrategie der Großeltern- und Elterngeneration für die Enkelgeneration im Ankunftsland dem Habitus der Notwendigkeit, den Bourdieu der Arbeiterklasse zuschreibt, zugeordnet werden kann, lässt sich hingegen das Freizeitverhalten der Familie Rosenthal dem Habitus der Distinktion zuordnen, der typisch für die herrschende Klasse ist. Ein weiterer Befund dieser Untersuchung ist, dass im Vergleich zur Enkelin Rosenthal bei der Enkelin Popow eine sogenannte Sphärendiskrepanz rekonstruiert wurde. So ist die Enkelin Popow in der äußeren Sphäre der Schule auf sich gestellt, da die Großeltern- und Elterngeneration zum deutschen Schulsystem nur über einen geringen Informationsstand verfügen. Die Enkelin grenzt sich einerseits von ihrer Familie (innere Sphäre) und deutschen Schulabbrechern (äußere Sphäre) ab, orientiert sich aber andererseits beim Versuch sozial aufzusteigen an russischsprachigen Peers, die die gymnasiale Oberstufe besuchen (dritte Sphäre). Bei Enkelin Popow fungiert demzufolge die Peergruppe und nicht die Familie als zentraler Bildungsort. An dieser Stelle sei angemerkt, dass sowohl bei einer russisch-jüdischen Familie als auch bei einer Spätaussiedlerfamilie der intergenerationale Bildungstransfer durch die Migration beeinflusst wurde. Während Familie Rosenthal in der Herkunftsgesellschaft der Intelligenzija zuzuordnen ist, gehört Familie Popow der Arbeiterschaft an. Daraus folgt, dass der intergenerationale Bildungstransfer der untersuchten Familien sowohl unabhängig vom Spätaussiedler- und Kontingentflüchtlingsstatus als auch vom herkunftsortspezifischen sozialen Status abläuft. Demnach kann geschlussfolgert werden, dass im Rahmen dieser Studie die Migration ein zentraler Faktor für den intergenerationalen Bildungstransfer ist.
In der Dissertationsarbeit mit dem Titel „Eine Hypothese über die Grundlagen von Moral und einige Implikationen“ unternimmt die Autorin den Versuch, die anthropologischen Prämissen moralischen Handelns herauszuarbeiten. Es wird eine Hypothese aufgestellt und erläutert, die behauptet, dass moralisches Handeln nur dann verständlich wird, wenn der Handelnde erstens die Fähigkeit der Phantasie aufweist, zweitens auf Erfahrungen (mittels seines Gedächtnisses) zugreifen kann und durch Konversation mit anderen Personen interagierte und interagiert, denn nur auf der Basis dieser drei Grundlagen von Moral können sich diejenigen Fähigkeiten ent¬wickeln, die als Voraussetzungen moralischen Handeln gesehen werden müssen: Selbstbewusstsein, Freiheit, die Entwicklung eines Wir-Gefühls, die Genese eines moralischen Ideals und die Fähigkeit, sich im Entscheiden und Handeln nach diesem Ideal richten zu können. Außerdem werden in dieser Dissertation einige Implikationen dieser Hypothese auf individueller und zwischenmenschlicher Ebene diskutiert.
Since half a century, cytometry has been a major scientific discipline in the field of cytomics - the study of system’s biology at single cell level. It enables the investigation of physiological processes, functional characteristics and rare events with proteins by analysing multiple parameters on an individual cell basis. In the last decade, mass cytometry has been established which increased the parallel measurement to up to 50 proteins. This has shifted the analysis strategy from conventional consecutive manual gates towards multi-dimensional data processing. Novel algorithms have been developed to tackle these high-dimensional protein combinations in the data. They are mainly based on clustering or non-linear dimension reduction techniques, or both, often combined with an upstream downsampling procedure. However, these tools have obstacles either in comprehensible interpretability, reproducibility, computational complexity or in comparability between samples and groups.
To address this bottleneck, a reproducible, semi-automated cytometric data mining workflow PRI (pattern recognition of immune cells) is proposed which combines three main steps: i) data preparation and storage; ii) bin-based combinatorial variable engineering of three protein markers, the so called triploTs, and subsequent sectioning of these triploTs in four parts; and iii) deployment of a data-driven supervised learning algorithm, the cross-validated elastic-net regularized logistic regression, with these triploT sections as input variables. As a result, the selected variables from the models are ranked by their prevalence, which potentially have discriminative value. The purpose is to significantly facilitate the identification of meaningful subpopulations, which are most distinguish between two groups. The proposed workflow PRI is exemplified by a recently published public mass cytometry data set. The authors found a T cell subpopulation which is discriminative between effective and ineffective treatment of breast carcinomas in mice. With PRI, that subpopulation was not only validated, but was further narrowed down as a particular Th1 cell population. Moreover, additional insights of combinatorial protein expressions are revealed in a traceable manner. An essential element in the workflow is the reproducible variable engineering. These variables serve as basis for a clearly interpretable visualization, for a structured variable exploration and as input layers in neural network constructs.
PRI facilitates the determination of marker levels in a semi-continuous manner. Jointly with the combinatorial display, it allows a straightforward observation of correlating patterns, and thus, the dominant expressed markers and cell hierarchies. Furthermore, it enables the identification and complex characterization of discriminating subpopulations due to its reproducible and pseudo-multi-parametric pattern presentation. This endorses its applicability as a tool for unbiased investigations on cell subsets within multi-dimensional cytometric data sets.
The immense popularity of online communication services in the last decade has not only upended our lives (with news spreading like wildfire on the Web, presidents announcing their decisions on Twitter, and the outcome of political elections being determined on Facebook) but also dramatically increased the amount of data exchanged on these platforms. Therefore, if we wish to understand the needs of modern society better and want to protect it from new threats, we urgently need more robust, higher-quality natural language processing (NLP) applications that can recognize such necessities and menaces automatically, by analyzing uncensored texts. Unfortunately, most NLP programs today have been created for standard language, as we know it from newspapers, or, in the best case, adapted to the specifics of English social media.
This thesis reduces the existing deficit by entering the new frontier of German online communication and addressing one of its most prolific forms—users’ conversations on Twitter. In particular, it explores the ways and means by how people express their opinions on this service, examines current approaches to automatic mining of these feelings, and proposes novel methods, which outperform state-of-the-art techniques. For this purpose, I introduce a new corpus of German tweets that have been manually annotated with sentiments, their targets and holders, as well as lexical polarity items and their contextual modifiers. Using these data, I explore four major areas of sentiment research: (i) generation of sentiment lexicons, (ii) fine-grained opinion mining, (iii) message-level polarity classification, and (iv) discourse-aware sentiment analysis. In the first task, I compare three popular groups of lexicon generation methods: dictionary-, corpus-, and word-embedding–based ones, finding that dictionary-based systems generally yield better polarity lists than the last two groups. Apart from this, I propose a linear projection algorithm, whose results surpass many existing automatically-generated lexicons. Afterwords, in the second task, I examine two common approaches to automatic prediction of sentiment spans, their sources, and targets: conditional random fields (CRFs) and recurrent neural networks, obtaining higher scores with the former model and improving these results even further by redefining the structure of CRF graphs. When dealing with message-level polarity classification, I juxtapose three major sentiment paradigms: lexicon-, machine-learning–, and deep-learning–based systems, and try to unite the first and last of these method groups by introducing a bidirectional neural network with lexicon-based attention. Finally, in order to make the new classifier aware of microblogs' discourse structure, I let it separately analyze the elementary discourse units of each tweet and infer the overall polarity of a message from the scores of its EDUs with the help of two new approaches: latent-marginalized CRFs and Recursive Dirichlet Process.
Die Wissenschaftsfreiheit ist ein Grundrecht, dessen Sinn und Auslegung im Rahmen von Reformen des Hochschulsystems nicht nur der Justiz, sondern auch der Wissenschaft selbst immer wieder Anlass zur Diskussion geben, so auch im Zuge der Einführung des so genannten Qualitätsmanagements von Studium und Lehre an deutschen Hochschulen. Die vorliegende Dissertationsschrift stellt die Ergebnisse einer empirischen Studie vor, die mit einer soziologischen Betrachtung des Qualitätsmanagements unterschiedlicher Hochschulen zu dieser Diskussion beiträgt.
Auf Grundlage der Prämisse, dass Verlauf und Folgen einer organisationalen Innovation nur verstanden werden können, wenn der alltägliche Umgang der Organisationsmitglieder mit den neuen Strukturen und Prozessen in die Analyse einbezogen wird, geht die Studie von der Frage aus, wie Akteurinnen und Akteure an deutschen Hochschulen die Qualitätsmanagementsysteme ihrer Organisationen nutzen. Die qualitative inhaltsanalytische Auswertung von 26 Leitfaden-Interviews mit Prorektorinnen und -rektoren, Qualitätsmanagement-Personal und Studiendekaninnen und -dekanen an neun Hochschulen ergibt, dass die Strategien der Akteursgruppen an den Hochschulen im Zusammenspiel mit strukturellen Aspekten unterschiedliche Dynamiken entstehen lassen, mit denen Implikationen für die Lehrfreiheit verbunden sind: Während die Autonomie der Lehrenden durch das Qualitätsmanagement an einigen Hochschulen unterstützt wird, sind sowohl Autonomie als auch Verantwortung für Studium und Lehre an anderen Hochschulen Gegenstand andauernder Konflikte, die auch das Qualitätsmanagement einschließen.
Business process management is an established technique for business organizations to manage and support their processes. Those processes are typically represented by graphical models designed with modeling languages, such as the Business Process Model and Notation (BPMN).
Since process models do not only serve the purpose of documentation but are also a basis for implementation and automation of the processes, they have to satisfy certain correctness requirements. In this regard, the notion of soundness of workflow nets was developed, that can be applied to BPMN process models in order to verify their correctness. Because the original soundness criteria are very restrictive regarding the behavior of the model, different variants of the soundness notion have been developed for situations in which certain violations are not even harmful.
All of those notions do only consider the control-flow structure of a process model, however. This poses a problem, taking into account the fact that with the recent release and the ongoing development of the Decision Model and Notation (DMN) standard, an increasing number of process models are complemented by respective decision models. DMN is a dedicated modeling language for decision logic and separates the concerns of process and decision logic into two different models, process and decision models respectively.
Hence, this thesis is concerned with the development of decisionaware soundness notions, i.e., notions of soundness that build upon the original soundness ideas for process models, but additionally take into account complementary decision models. Similar to the various notions of workflow net soundness, this thesis investigates different notions of decision soundness that can be applied depending on the desired degree of restrictiveness. Since decision tables are a standardized means of DMN to represent decision logic, this thesis also puts special focus on decision tables, discussing how they can be translated into an unambiguous format and how their possible output values can be efficiently determined.
Moreover, a prototypical implementation is described that supports checking a basic version of decision soundness. The decision soundness notions were also empirically evaluated on models from participants of an online course on process and decision modeling as well as from a process management project of a large insurance company. The evaluation demonstrates that violations of decision soundness indeed occur and can be detected with our approach.
There is evidence that infants start extracting words from fluent speech around 7.5 months of age (e.g., Jusczyk & Aslin, 1995) and that they use at least two mechanisms to segment words forms from fluent speech: prosodic information (e.g., Jusczyk, Cutler & Redanz, 1993) and statistical information (e.g., Saffran, Aslin & Newport, 1996). However, how these two mechanisms interact and whether they change during development is still not fully understood.
The main aim of the present work is to understand in what way different cues to word segmentation are exploited by infants when learning the language in their environment, as well as to explore whether this ability is related to later language skills. In Chapter 3 we pursued to determine the reliability of the method used in most of the experiments in the present thesis (the Headturn Preference Procedure), as well as to examine correlations and individual differences between infants’ performance and later language outcomes. In Chapter 4 we investigated how German-speaking adults weigh statistical and prosodic information for word segmentation. We familiarized adults with an auditory string in which statistical and prosodic information indicated different word boundaries and obtained both behavioral and pupillometry responses. Then, we conducted further experiments to understand in what way different cues to word segmentation are exploited by 9-month-old German-learning infants (Chapter 5) and by 6-month-old German-learning infants (Chapter 6). In addition, we conducted follow-up questionnaires with the infants and obtained language outcomes at later stages of development.
Our findings from this thesis revealed that (1) German-speaking adults show a strong weight of prosodic cues, at least for the materials used in this study and that (2) German-learning infants weight these two kind of cues differently depending on age and/or language experience. We observed that, unlike English-learning infants, 6-month-old infants relied more strongly on prosodic cues. Nine-month-olds do not show any preference for either of the cues in the word segmentation task. From the present results it remains unclear whether the ability to use prosodic cues to word segmentation relates to later language vocabulary. We speculate that prosody provides infants with their first window into the specific acoustic regularities in the signal, which enables them to master the specific stress pattern of German rapidly. Our findings are a step forwards in the understanding of an early impact of the native prosody compared to statistical learning in early word segmentation.
Data assimilation has been an active area of research in recent years, owing to its wide utility. At the core of data assimilation are filtering, prediction, and smoothing procedures. Filtering entails incorporation of measurements' information into the model to gain more insight into a given state governed by a noisy state space model. Most natural laws are governed by time-continuous nonlinear models. For the most part, the knowledge available about a model is incomplete; and hence uncertainties are approximated by means of probabilities. Time-continuous filtering, therefore, holds promise for wider usefulness, for it offers a means of combining noisy measurements with imperfect model to provide more insight on a given state.
The solution to time-continuous nonlinear Gaussian filtering problem is provided for by the Kushner-Stratonovich equation. Unfortunately, the Kushner-Stratonovich equation lacks a closed-form solution. Moreover, the numerical approximations based on Taylor expansion above third order are fraught with computational complications. For this reason, numerical methods based on Monte Carlo methods have been resorted to. Chief among these methods are sequential Monte-Carlo methods (or particle filters), for they allow for online assimilation of data. Particle filters are not without challenges: they suffer from particle degeneracy, sample impoverishment, and computational costs arising from resampling.
The goal of this thesis is to:— i) Review the derivation of Kushner-Stratonovich equation from first principles and its extant numerical approximation methods, ii) Study the feedback particle filters as a way of avoiding resampling in particle filters, iii) Study joint state and parameter estimation in time-continuous settings, iv) Apply the notions studied to linear hyperbolic stochastic differential equations.
The interconnection between Itô integrals and stochastic partial differential equations and those of Stratonovich is introduced in anticipation of feedback particle filters. With these ideas and motivated by the variants of ensemble Kalman-Bucy filters founded on the structure of the innovation process, a feedback particle filter with randomly perturbed innovation is proposed. Moreover, feedback particle filters based on coupling of prediction and analysis measures are proposed. They register a better performance than the bootstrap particle filter at lower ensemble sizes.
We study joint state and parameter estimation, both by means of extended state spaces and by use of dual filters. Feedback particle filters seem to perform well in both cases. Finally, we apply joint state and parameter estimation in the advection and wave equation, whose velocity is spatially varying. Two methods are employed: Metropolis Hastings with filter likelihood and a dual filter comprising of Kalman-Bucy filter and ensemble Kalman-Bucy filter. The former performs better than the latter.
The fabrication of 1D nanostrands composed of stimuli responsive microgels has been shown in this work. Microgels are well known materials able to respond to various stimuli from outer environment. Since these microgels respond via a volume change to an external stimulus, a targeted mechanical response can be achieved. Through carefully choosing the right composition of the polymer matrix, microgels can be designed to react precisely to the targeted stimuli (e.g. drug delivery via pH and temperature changes, or selective contractions through changes in electrical current125).
In this work, it was aimed to create flexible nano-filaments which are capable of fast anisotropic contractions similar to muscle filaments. For the fabrication of such filaments or strands, nanostructured templates (PDMS wrinkles) were chosen due to a facile and low-cost fabrication and versatile tunability of their dimensions. Additionally, wrinkling is a well-known lithography-free method which enables the fabrication of nanostructures in a reproducible manner and with a high long-range periodicity.
In Chapter 2.1, it was shown for the first time that microgels as soft matter particles can be aligned to densely packed microgel arrays of various lateral dimensions. The alignment of microgels with different compositions (e.g. VCL/AAEM, NIPAAm, NIPAAm/VCL and charged microgels) was shown by using different assembly techniques (e.g. spin-coating, template confined molding). It was chosen to set one experimental parameter constant which was the SiOx surface composition of the templates and substrates (e.g. oxidized PDMS wrinkles, Si-wafers and glass slides). It was shown that the fabrication of nanoarrays was feasible with all tested microgel types. Although the microgels exhibited different deformability when aligned on a flat surface, they retained their thermo-responsivity and swelling behavior.
Towards the fabrication of 1D microgel strands interparticle connectivity was aspired. This was achieved via different cross-linking methods (i.e. cross-linking via UV-irradiation and host-guest complexation) discussed in Chapter 2.2. The microgel arrays created by different assembly methods and microgel types were tested for their cross-linking suitability. It was observed that NIPAAm based microgels cannot be cross-linked with UV light. Furthermore, it was found that these microgels exhibit a strong surface-particle-interaction and therefore could not be detached from the given substrates. In contrast to the latter, with VCL/AAEM based microgels it was possible to both UV cross-link them based on the keto-enol tautomerism of the AAEM copolymer, and to detach them from the substrate due to the lower adhesion energy towards SiOx surfaces. With VCL/AAEM microgels long, one-dimensional microgel strands could be re-dispersed in water for further analysis. It has also been shown that at least one lateral dimension of the free dispersed 1D microgel strands is easily controllable by adjusting the wavelength of the wrinkled template. For further work, only VCL/AAEM based microgels were used to focus on the main aim of this work, i.e. the fabrication of 1D microgel nanostrands.
As an alternative to the unspecific and harsh UV cross-linking, the host-guest complexation via diazobenzene cross-linkers and cyclodextrin hosts was explored. The idea behind this approach was to give means to a future construction kit-like approach by incorporation of cyclodextrin comonomers in a broad variety of particle systems (e.g. microgels, nanoparticles). For this purpose, VCL/AAEM microgels were copolymerized with different amounts of mono-acrylate functionalized β-cyclodextrin (CD). After successfully testing the cross-linking capability in solution, the cross-linking of aligned VCL/AAEM/CD microgels was tried. Although the cross-linking worked well, once the single arrays came into contact to each other, they agglomerated. As a reason for this behavior residual amounts of mono-complexed diazobenzene linkers were suspected. Thus, end-capping strategies were tried out (e.g. excess amounts of β-cyclodextrin and coverage with azobenzene functionalized AuNPs) but were unsuccessful. With deeper thought, entropy effects were taken into consideration which favor the release of complexed diazobenzene linker leading to agglomerations. To circumvent this entropy driven effect, a multifunctional polymer with 50% azobenzene groups (Harada polymer) was used. First experiments with this polymer showed promising results regarding a less pronounced agglomeration (Figure 77). Thus, this approach could be pursued in the future. In this chapter it was found out that in contrast to pearl necklace and ribbon like formations, particle alignment in zigzag formation provided the best compromise in terms of stability in dispersion (see Figure 44a and Figure 51) while maintaining sufficient flexibility.
For this reason, microgel strands in zigzag formation were used for the motion analysis described in Chapter 2.3. The aim was to observe the properties of unrestrained microgel strands in solution (e.g. diffusion behavior, rotational properties and ideally, anisotropic contraction after temperature increase). Initially, 1D microgel strands were manipulated via AFM in a liquid cell setup. It could be observed that the strands required a higher load force compared to single microgels to be detached from the surface. However, with the AFM it was not possible to detach the strands in a controllable manner but resulted in a complete removal of single microgel particles and a tearing off the strands from the surface, respectively. For this reason, to observe the motion behavior of unrestrained microgel strands in solution, confocal microscopy was used. Furthermore, to hinder an adsorption of the strands, it was found out that coating the surface of the substrates with a repulsive polymer film was beneficial. Confocal and wide-field microscopy videos showed that the microgel strands exhibit translational and rotational diffusive motion in solution without perceptible bending. Unfortunately, with these methods the detection of the anisotropic stimuli responsive contraction of the free moving microgel strands was not possible. To summarize, the flexibility of microgel strands is more comparable to the mechanical behavior of a semi flexible cable than to a yarn. The strands studied here consist of dozens or even hundreds of discrete submicron units strung together by cross-linking, having few parallels in nanotechnology.
With the insights gained in this work on microgel-surface interactions, in the future, a targeted functionalization of the template and substrate surfaces can be conducted to actively prevent unwanted microgel adsorption for a given microgel system (e.g. PVCL and polystyrene coating235). This measure would make the discussed alignment methods more diverse. As shown herein, the assembly methods enable a versatile microgel alignment (e.g. microgel meshes, double and triple strands). To go further, one could use more complex templates (e.g. ceramic rhombs and star shaped wrinkles (Figure 14) to expand the possibilities of microgel alignment and to precisely control their aspect ratios (e.g. microgel rods with homogeneous size distributions).
Supermassive black holes reside in the hearts of almost all massive galaxies. Their evolutionary path seems to be strongly linked to the evolution of their host galaxies, as implied by several empirical relations between the black hole mass (M BH ) and different host galaxy properties. The physical driver of this co-evolution is, however, still not understood. More mass measurements over homogeneous samples and a detailed understanding of systematic uncertainties are required to fathom the origin of the scaling relations.
In this thesis, I present the mass estimations of supermassive black holes in the nuclei of one late-type and thirteen early-type galaxies. Our SMASHING sample extends from the intermediate to the massive galaxy mass regime and was selected to fill in gaps in number of galaxies along the scaling relations. All galaxies were observed at high spatial resolution, making use of the adaptive-optics mode of integral field unit (IFU) instruments on state-of-the-art telescopes (SINFONI, NIFS, MUSE). I extracted the stellar kinematics from these observations and constructed dynamical Jeans and Schwarzschild models to estimate the mass of the central black holes robustly. My new mass estimates increase the number of early-type galaxies with measured black hole masses by 15%. The seven measured galaxies with nuclear light deficits (’cores’) augment the sample of cored galaxies with measured black holes by 40%. Next to determining massive black hole masses, evaluating the accuracy of black hole masses is crucial for understanding the intrinsic scatter of the black hole- host galaxy scaling relations. I tested various sources of systematic uncertainty on my derived mass estimates.
The M BH estimate of the single late-type galaxy of the sample yielded an upper limit, which I could constrain very robustly. I tested the effects of dust, mass-to-light ratio (M/L) variation, and dark matter on my measured M BH . Based on these tests, the typically assumed constant M/L ratio can be an adequate assumption to account for the small amounts of dark matter in the center of that galaxy. I also tested the effect of a variable M/L variation on the M BH measurement on a second galaxy. By considering stellar M/L variations in the dynamical modeling, the measured M BH decreased by 30%. In the future, this test should be performed on additional galaxies to learn how an as constant assumed M/L flaws the estimated black hole masses.
Based on our upper limit mass measurement, I confirm previous suggestions that resolving the predicted BH sphere-of-influence is not a strict condition to measure black hole masses. Instead, it is only a rough guide for the detection of the black hole if high-quality, and high signal-to-noise IFU data are used for the measurement. About half of our sample consists of massive early-type galaxies which show nuclear surface brightness cores and signs of triaxiality. While these types of galaxies are typically modeled with axisymmetric modeling methods, the effects on M BH are not well studied yet. The massive galaxies of our presented galaxy sample are well suited to test the effect of different stellar dynamical models on the measured black hole mass in evidently triaxial galaxies. I have compared spherical Jeans and axisymmetric Schwarzschild models and will add triaxial Schwarzschild models to this comparison in the future. The constructed Jeans and Schwarzschild models mostly disagree with each other and cannot reproduce many of the triaxial features of the galaxies (e.g., nuclear sub-components, prolate rotation). The consequence of the axisymmetric-triaxial assumption on the accuracy of M BH and its impact on the black hole - host galaxy relation needs to be carefully examined in the future.
In the sample of galaxies with published M BH , we find measurements based on different dynamical tracers, requiring different observations, assumptions, and methods. Crucially, different tracers do not always give consistent results. I have used two independent tracers (cold molecular gas and stars) to estimate M BH in a regular galaxy of our sample. While the two estimates are consistent within their errors, the stellar-based measurement is twice as high as the gas-based. Similar trends have also been found in the literature. Therefore, a rigorous test of the systematics associated with the different modeling methods is required in the future. I caution to take the effects of different tracers (and methods) into account when discussing the scaling relations.
I conclude this thesis by comparing my galaxy sample with the compilation of galaxies with measured black holes from the literature, also adding six SMASHING galaxies, which were published outside of this thesis. None of the SMASHING galaxies deviates significantly from the literature measurements. Their inclusion to the published early-type galaxies causes a change towards a shallower slope for the M BH - effective velocity dispersion relation, which is mainly driven by the massive galaxies of our sample. More unbiased and homogenous measurements are needed in the future to determine the shape of the relation and understand its physical origin.
For many years, psycholinguistic evidence has been predominantly based on findings from native speakers of Indo-European languages, primarily English, thus providing a rather limited perspective into the human language system. In recent years a growing body of experimental research has been devoted to broadening this picture, testing a wide range of speakers and languages, aiming to understanding the factors that lead to variability in linguistic performance. The present dissertation investigates sources of variability within the morphological domain, examining how and to what extent morphological processes and representations are shaped by specific properties of languages and speakers. Firstly, the present work focuses on a less explored language, Hebrew, to investigate how the unique non-concatenative morphological structure of Hebrew, namely a non-linear combination of consonantal roots and vowel patterns to form lexical entries (L-M-D + CiCeC = limed ‘teach’), affects morphological processes and representations in the Hebrew lexicon. Secondly, a less investigated population was tested: late learners of a second language. We directly compare native (L1) and non-native (L2) speakers, specifically highly proficient and immersed late learners of Hebrew. Throughout all publications, we have focused on a morphological phenomenon of inflectional classes (called binyanim; singular: binyan), comparing productive (class Piel, e.g., limed ‘teach’) and unproductive (class Paal, e.g., lamad ‘learn’) verbal inflectional classes. By using this test case, two psycholinguistic aspects of morphology were examined: (i) how morphological structure affects online recognition of complex words, using masked priming (Publications I and II) and cross-modal priming (Publication III) techniques, and (ii) what type of cues are used when extending morpho-phonological patterns to novel complex forms, a process referred to as morphological generalization, using an elicited production task (Publication IV).
The findings obtained in the four manuscripts, either published or under review, provide significant insights into the role of productivity in Hebrew morphological processing and generalization in L1 and L2 speakers. Firstly, the present L1 data revealed a close relationship between productivity of Hebrew verbal classes and recognition process, as revealed in both priming techniques. The consonantal root was accessed only in the productive class (Piel) but not the unproductive class (Paal). Another dissociation between the two classes was revealed in the cross-modal priming, yielding a semantic relatedness effect only for Paal but not Piel primes. These findings are taken to reflect that the Hebrew mental representations display a balance between stored undecomposable unstructured stems (Paal) and decomposed structured stems (Piel), in a similar manner to a typical dual-route architecture, showing that the Hebrew mental lexicon is less unique than previously claimed in psycholinguistic research. The results of the generalization study, however, indicate that there are still substantial differences between inflectional classes of Hebrew and other Indo-European classes, particularly in the type of information they rely on in generalization to novel forms. Hebrew binyan generalization relies more on cues of argument structure and less on phonological cues.
Secondly, clear L1/L2 differences were observed in the sensitivity to abstract morphological and morpho-syntactic information during complex word recognition and generalization. While L1 Hebrew speakers were sensitive to the binyan information during recognition, expressed by the contrast in root priming, L2 speakers showed similar root priming effects for both classes, but only when the primes were presented in an infinitive form. A root priming effect was not obtained for primes in a finite form. These patterns are interpreted as evidence for a reduced sensitivity of L2 speakers to morphological information, such as information about inflectional classes, and evidence for processing costs in recognition of forms carrying complex morpho-syntactic information. Reduced reliance on structural information cues was found in production of novel verbal forms, when the L2 group displayed a weaker effect of argument structure for Piel responses, in comparison to the L1 group. Given the L2 results, we suggest that morphological and morphosyntactic information remains challenging for late bilinguals, even at high proficiency levels.
The Central Andes host large reserves of base and precious metals. The region represented, in 2017, an important part of the worldwide mining activity. Three principal types of deposits have been identified and studied: 1) porphyry type deposits extending from central Chile and Argentina to Bolivia, and Northern Peru, 2) iron oxide-copper-gold (IOCG) deposits, extending from central Peru to central Chile, and 3) epithermal tin polymetallic deposits extending from Southern Peru to Northern Argentina, which compose a large part of the deposits of the Bolivian Tin Belt (BTB). Deposits in the BTB can be divided into two major types: (1) tin-tungsten-zinc pluton-related polymetallic deposits, and (2) tin-silver-lead-zinc epithermal polymetallic vein deposits.
Mina Pirquitas is a tin-silver-lead-zinc epithermal polymetallic vein deposit, located in north-west Argentina, that used to be one of the most important tin-silver producing mine of the country. It was interpreted to be part of the BTB and it shares similar mineral associations with southern pluton related BTB epithermal deposits. Two major mineralization events related to three pulses of magmatic fluids mixed with meteoric water have been identified. The first event can be divided in two stages: 1) stage I-1 with quartz, pyrite, and cassiterite precipitating from fluids between 233 and 370 °C and salinity between 0 and 7.5 wt%, corresponding to a first pulse of fluids, and 2) stage I-2 with sphalerite and tin-silver-lead-antimony sulfosalts precipitating from fluids between 213 and 274 °C with salinity up to 10.6 wt%, corresponding to a new pulse of magmatic fluids in the hydrothermal system. The mineralization event II deposited the richest silver ores at Pirquitas. Event II fluids temperatures and salinities range between 190 and 252 °C and between 0.9 and 4.3 wt% respectively. This corresponds to the waning supply of magmatic fluids. Noble gas isotopic compositions and concentrations in ore-hosted fluid inclusions demonstrate a significant contribution of magmatic fluids to the Pirquitas mineralization although no intrusive rocks are exposed in the mine area.
Lead and sulfur isotopic measurements on ore minerals show that Pirquitas shares a similar signature with southern pluton related polymetallic deposits in the BTB. Furthermore, the major part of the sulfur isotopic values of sulfide and sulfosalt minerals from Pirquitas ranges in the field for sulfur derived from igneous rocks. This suggests that the main contribution of sulfur to the hydrothermal system at Pirquitas is likely to be magma-derived. The precise age of the deposit is still unknown but the results of wolframite dating of 2.9 ± 9.1 Ma and local structural observations suggest that the late mineralization event is younger than 12 Ma.
Over the last years there is an increasing awareness that historical land cover changes and associated land use legacies may be important drivers for present-day species richness and biodiversity due to time-delayed extinctions or colonizations in response to historical environmental changes. Historically altered habitat patches may therefore exhibit an extinction debt or colonization credit and can be expected to lose or gain species in the future. However, extinction debts and colonization credits are difficult to detect and their actual magnitudes or payments have rarely been quantified because species richness patterns and dynamics are also shaped by recent environmental conditions and recent environmental changes.
In this thesis we aimed to determine patterns of herb-layer species richness and recent species richness dynamics of forest herb layer plants and link those patterns and dynamics to historical land cover changes and associated land use legacies. The study was conducted in the Prignitz, NE-Germany, where the forest distribution remained stable for the last ca. 100 years but where a) the deciduous forest area had declined by more than 90 per cent (leaving only remnants of "ancient forests"), b) small new forests had been established on former agricultural land ("post-agricultural forests"). Here, we analyzed the relative importance of land use history and associated historical land cover changes for herb layer species richness compared to recent environmental factors and determined magnitudes of extinction debt and colonization credit and their payment in ancient and post-agricultural forests, respectively.
We showed that present-day species richness patterns were still shaped by historical land cover changes that ranged back to more than a century. Although recent environmental conditions were largely comparable we found significantly more forest specialists, species with short-distance dispersal capabilities and clonals in ancient forests than in post-agricultural forests. Those species richness differences were largely contingent to a colonization credit in post-agricultural forests that ranged up to 9 species (average 4.7), while the extinction debt in ancient forests had almost completely been paid. Environmental legacies from historical agricultural land use played a minor role for species richness differences. Instead, patch connectivity was most important. Species richness in ancient forests was still dependent on historical connectivity, indicating a last glimpse of an extinction debt, and the colonization credit was highest in isolated post-agricultural forests. In post-agricultural forests that were better connected or directly adjacent to ancient forest patches the colonization credit was way smaller and we were able to verify a gradual payment of the colonization credit from 2.7 species to 1.5 species over the last six decades.
This is a publication-based dissertation comprising three original research stud-ies (one published, one submitted and one ready for submission; status March 2019). The dissertation introduces a generic computer model as a tool to investigate the behaviour and population dynamics of animals in cyclic environments. The model is further employed for analysing how migratory birds respond to various scenarios of altered food supply under global change. Here, ecological and evolutionary time-scales are considered, as well as the biological constraints and trade-offs the individual faces, which ultimately shape response dynamics at the population level. Further, the effect of fine-scale temporal patterns in re-source supply are studied, which is challenging to achieve experimentally. My findings predict population declines, altered behavioural timing and negative carry-over effects arising in migratory birds under global change. They thus stress the need for intensified research on how ecological mechanisms are affected by global change and for effective conservation measures for migratory birds. The open-source modelling software created for this dissertation can now be used for other taxa and related research questions. Overall, this thesis improves our mechanistic understanding of the impacts of global change on migratory birds as one prerequisite to comprehend ongoing global biodiversity loss. The research results are discussed in a broader ecological and scientific context in a concluding synthesis chapter.
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.
The Government will create a motivated, merit-based, performance-driven, and professional civil service that is resistant to temptations of corruption and which provides efficient, effective and transparent public services that do not force customers to pay bribes.
— (GoIRA, 2006, p. 106)
We were in a black hole! We had an empty glass and had nothing from our side to fill it with! Thus, we accepted anything anybody offered; that is how our glass was filled; that is how we reformed our civil service.
— (Former Advisor to IARCSC, personal communication, August 2015)
How and under what conditions were the post-Taleban Civil Service Reforms of Afghanistan initiated? What were the main components of the reforms? What were their objectives and to which extent were they achieved? Who were the leading domestic and foreign actors involved in the process? Finally, what specific factors influenced the success and failure Afghanistan’s Civil Service Reforms since 2002? Guided by such fundamental questions, this research studies the wicked process of reforming the Afghan civil service in an environment where a variety of contextual, programmatic, and external factors affected the design and implementation of reforms that were entirely funded and technically assisted by the international community.
Focusing on the core components of reforms—recruitment, remuneration, and appraisal of civil servants—the qualitative study provides a detailed picture of the pre-reform civil service and its major human resources developments in the past. Following discussions on the content and purposes of the main reform programs, it will then analyze the extent of changes in policies and practices by examining the outputs and effects of these reforms.
Moreover, the study defines the specific factors that led the reforms toward a situation where most of the intended objectives remain unachieved. Doing so, it explores and explains how an overwhelming influence of international actors with conflicting interests, large-scale corruption, political interference, networks of patronage, institutionalized nepotism, culturally accepted cronyism and widespread ethnic favoritism created a very complex environment and prevented the reforms from transforming Afghanistan’s patrimonial civil service into a professional civil service, which is driven by performance and merit.
The North China Plain (NCP) is one of the most productive and intensive agricultural regions in China. High doses of mineral nitrogen (N) fertiliser, often combined with flood irrigation, are applied, resulting in N surplus, groundwater depletion and environmental pollution. The objectives of this thesis were to use the HERMES model to simulate the N cycle in winter wheat (Triticum aestivum L.)–summer maize (Zea mays L.) double crop rotations and show the performance of the HERMES model, of the new ammonia volatilisation sub-module and of the new nitrification inhibition tool in the NCP. Further objectives were to assess the models potential to save N and water on plot and county scale, as well as on short and long-term. Additionally, improved management strategies with the help of a model-based nitrogen fertiliser recommendation (NFR) and adapted irrigation, should be found.
Results showed that the HERMES model performed well under growing conditions of the NCP and was able to describe the relevant processes related to soil–plant interactions concerning N and water during a 2.5 year field experiment. No differences in grain yield between the real-time model-based NFR and the other treatments of the experiments on plot scale in Quzhou County could be found. Simulations with increasing amounts of irrigation resulted in significantly higher N leaching, higher N requirements of the NFR and reduced yields. Thus, conventional flood irrigation as currently practised by the farmers bears great uncertainties and exact irrigation amounts should be known for future simulation studies. In the best-practice scenario simulation on plot-scale, N input and N leaching, but also irrigation water could be reduced strongly within 2 years. Thus, the model-based NFR in combination with adapted irrigation had the highest potential to reduce nitrate leaching, compared to farmers practice and mineral N (Nmin)-reduced treatments. Also the calibrated and validated ammonia volatilisation sub-module of the HERMES model worked well under the climatic and soil conditions of northern China. Simple ammonia volatilisation approaches gave also satisfying results compared to process-oriented approaches. During the simulation with Ammonium sulphate Nitrate with nitrification inhibitor (ASNDMPP) ammonia volatilisation was higher than in the simulation without nitrification inhibitor, while the result for nitrate leaching was the opposite. Although nitrification worked well in the model, nitrification-born nitrous oxide emissions should be considered in future. Results of the simulated annual long-term (31 years) N losses in whole Quzhou County in Hebei Province were 296.8 kg N ha−1 under common farmers practice treatment and 101.7 kg N ha−1 under optimised treatment including NFR and automated irrigation (OPTai). Spatial differences in simulated N losses throughout Quzhou County, could only be found due to different N inputs. Simulations of an optimised treatment, could save on average more than 260 kg N ha−1a−1 from fertiliser input and 190 kg N ha−1a−1 from N losses and around 115.7 mm a−1 of water, compared to farmers practice. These long-term simulation results showed lower N and water saving potential, compared to short-term simulations and underline the necessity of long-term simulations to overcome the effect of high initial N stocks in soil.
Additionally, the OPTai worked best on clay loam soil except for a high simulated denitrification loss, while the simulations using farmers practice irrigation could not match the actual water needs resulting in yield decline, especially for winter wheat. Thus, a precise adaption of management to actual weather conditions and plant growth needs is necessary for future simulations. However, the optimised treatments did not seem to be able to maintain the soil organic matter pools, even with full crop residue input. Extra organic inputs seem to be required to maintain soil quality in the optimised treatments.
HERMES is a relatively simple model, with regard to data input requirements, to simulate the N cycle. It can offer interpretation of management options on plot, on county and regional scale for extension and research staff. Also in combination with other N and water saving methods the model promises to be a useful tool.
Analysis of supramolecular assemblies of NE81, the first lamin protein in a non-metazoan organism
(2019)
Nuclear lamins are nucleus-specific intermediate filaments forming a network located at the inner nuclear membrane of the nuclear envelope. They form the nuclear lamina together with proteins of the inner nuclear membrane regulating nuclear shape and gene expression, among others. The amoebozoan Dictyostelium NE81 protein is a suitable candidate for an evolutionary conserved lamin protein in this non-metazoan organism. It shares the domain organization of metazoan lamins and is fulfilling major lamin functions in Dictyostelium. Moreover, field-emission scanning electron microscopy (feSEM) images of NE81 expressed on Xenopus oocytes nuclei revealed filamentous structures with an overall appearance highly reminiscent to that of metazoan Xenopus lamin B2. For the classification as a lamin-like or a bona fide lamin protein, a better understanding of the supramolecular NE81 structure was necessary. Yet, NE81 carrying a large N-terminal GFP-tag turned out as unsuitable source for protein isolation and characterization; GFP-NE81 expressed in Dictyostelium NE81 knock-out cells exhibited an abnormal distribution, which is an indicator for an inaccurate assembly of GFP-tagged NE81. Hence, a shorter 8×HisMyc construct was the tag of choice to investi-gate formation and structure of NE81 assemblies. One strategy was the structural analysis of NE81 in situ at the outer nuclear membrane in Dictyostelium cells; NE81 without a func-tional nuclear localization signal (NLS) forms assemblies at the outer face of the nucleus. Ultrastructural feSEM pictures of NE81ΔNLS nuclei showed a few filaments of the expected size but no repetitive filamentous structures. The former strategy should also be established for metazoan lamins in order to facilitate their structural analysis. However, heterologously expressed Xenopus and C. elegans lamins showed no uniform localization at the outer nucle-ar envelope of Dictyostelium and hence, no further ultrastructural analysis was undertaken. For in vitro assembly experiments a Dictyostelium mutant was generated, expressing NE81 without the NLS and the membrane-anchoring isoprenylation site (HisMyc-NE81ΔNLSΔCLIM). The cytosolic NE81 clusters were soluble at high ionic strength and were purified from Dictyostelium extracts using Ni-NTA Agarose. Widefield immunofluorescence microscopy, super-resolution light microscopy and electron microscopy images of purified NE81 showed its capability to form filamentous structures at low ionic strength, as described previously for metazoan lamins. Introduction of a phosphomimetic point mutation (S122E) into the CDK1-consensus sequence of NE81 led to disassembled NE81 protein in vivo, which could be reversibly stimulated to form supramolecular assemblies by blue light exposure.
The results of this work reveal that NE81 has to be considered a bona fide lamin, since it is able to form filamentous assemblies. Furthermore, they highlight Dictyostelium as a non-mammalian model organism with a well-characterized nuclear envelope containing all rele-vant protein components known in animal cells.
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.
Predation drives coexistence, evolution and population dynamics of species in food webs, and has strong impacts on related ecosystem functions (e.g. primary production). The effect of predation on these processes largely depends on the trade-offs between functional traits in the predator and prey community. Trade-offs between defence against predation and competitive ability, for example, allow for prey speciation and predator-mediated coexistence of prey species with different strategies (defended or competitive), which may stabilize the overall food web dynamics. While the importance of such trade-offs for coexistence is widely known, we lack an understanding and the empirical evidence of how the variety of differently shaped trade-offs at multiple trophic levels affect biodiversity, trait adaptation and biomass dynamics in food webs. Such mechanistic understanding is crucial for predictions and management decisions that aim to maintain biodiversity and the capability of communities to adapt to environmental change ensuring their persistence.
In this dissertation, after a general introduction to predator-prey interactions and tradeoffs, I first focus on trade-offs in the prey between qualitatively different types of defence (e.g. camouflage or escape behaviour) and their costs. I show that these different types lead to different patterns of predator-mediated coexistence and population dynamics, by using a simple predator-prey model. In a second step, I elaborate quantitative aspects of trade-offs and demonstrates that the shape of the trade-off curve in combination with trait-fitness relationships strongly affects competition among different prey types: Either specialized species with extreme trait combinations (undefended or completely defended) coexist, or a species with an intermediate defence level dominates. The developed theory on trade-off shapes and coexistence is kept general, allowing for applications apart from defence-competitiveness trade-offs. Thirdly, I tested the theory on trade-off shapes on a long-term field data set of phytoplankton from Lake Constance. The measured concave trade-off between defence and growth governs seasonal trait changes of phytoplankton in response to an altering grazing pressure by zooplankton, and affects the maintenance of trait variation in the community. In a fourth step, I analyse the interplay of different tradeoffs at multiple trophic levels with plankton data of Lake Constance and a corresponding tritrophic food web model. The results show that the trait and biomass dynamics of the different three trophic levels are interrelated in a trophic biomass-trait cascade, leading to unintuitive patterns of trait changes that are reversed in comparison to predictions from bitrophic systems. Finally, in the general discussion, I extract main ideas on trade-offs in multitrophic systems, develop a graphical theory on trade-off-based coexistence, discuss the interplay of intra- and interspecific trade-offs, and end with a management-oriented view on the results of the dissertation, describing how food webs may respond to future global changes, given their trade-offs.
Predator-prey interactions provide central links in food webs. These interaction are directly or indirectly impacted by a number of factors. These factors range from physiological characteristics of individual organisms, over specifics of their interaction to impacts of the environment. They may generate the potential for the application of different strategies by predators and prey. Within this thesis, I modelled predator-prey interactions and investigated a broad range of different factors driving the application of certain strategies, that affect the individuals or their populations. In doing so, I focused on phytoplankton-zooplankton systems as established model systems of predator-prey interactions.
At the level of predator physiology I proposed, and partly confirmed, adaptations to fluctuating availability of co-limiting nutrients as beneficial strategies. These may allow to store ingested nutrients or to regulate the effort put into nutrient assimilation. We found that these two strategies are beneficial at different fluctuation frequencies of the nutrients, but may positively interact at intermediate frequencies. The corresponding experiments supported our model results. We found that the temporal structure of nutrient fluctuations indeed has strong effects on the juvenile somatic growth rate of {\itshape Daphnia}.
Predator colimitation by energy and essential biochemical nutrients gave rise to another physiological strategy. High-quality prey species may render themselves indispensable in a scenario of predator-mediated coexistence by being the only source of essential biochemical nutrients, such as cholesterol. Thereby, the high-quality prey may even compensate for a lacking defense and ensure its persistence in competition with other more defended prey species.
We found a similar effect in a model where algae and bacteria compete for nutrients. Now, being the only source of a compound that is required by the competitor (bacteria) prevented the competitive exclusion of the algae. In this case, the essential compounds were the organic carbon provided by the algae. Here again, being indispensable served as a prey strategy that ensured its coexistence.
The latter scenario also gave rise to the application of the two metabolic strategies of autotrophy and heterotrophy by algae and bacteria, respectively. We found that their coexistence allowed the recycling of resources in a microbial loop that would otherwise be lost. Instead, these resources were made available to higher trophic levels, increasing the trophic transfer efficiency in food webs.
The predation process comprises the next higher level of factors shaping the predator-prey interaction, besides these factors that originated from the functioning or composition of individuals. Here, I focused on defensive mechanisms and investigated multiple scenarios of static or adaptive combinations of prey defense and predator offense. I confirmed and extended earlier reports on the coexistence-promoting effects of partially lower palatability of the prey community. When bacteria and algae are coexisting, a higher palatability of bacteria may increase the average predator biomass, with the side effect of making the population dynamics more regular. This may facilitate experimental investigations and interpretations. If defense and offense are adaptive, this allows organisms to maximize their growth rate. Besides this fitness-enhancing effect, I found that co-adaptation may provide the predator-prey system with the flexibility to buffer external perturbations.
On top of these rather internal factors, environmental drivers also affect predator-prey interactions. I showed that environmental nutrient fluctuations may create a spatio-temporal resource heterogeneity that selects for different predator strategies. I hypothesized that this might favour either storage or acclimation specialists, depending on the frequency of the environmental fluctuations.
We found that many of these factors promote the coexistence of different strategies and may therefore support and sustain biodiversity. Thus, they might be relevant for the maintenance of crucial ecosystem functions that also affect us humans. Besides this, the richness of factors that impact predator-prey interactions might explain why so many species, especially in the planktonic regime, are able to coexist.
Most of the matter in the universe consists of hydrogen. The hydrogen in the intergalactic medium (IGM), the matter between the galaxies, underwent a change of its ionisation state at the epoch of reionisation, at a redshift roughly between 6>z>10, or ~10^8 years after the Big Bang. At this time, the mostly neutral hydrogen in the IGM was ionised but the source of the responsible hydrogen ionising emission remains unclear. In this thesis I discuss the most likely candidates for the emission of this ionising radiation, which are a type of galaxy called Lyman alpha emitters (LAEs). As implied by their name, they emit Lyman alpha radiation, produced after a hydrogen atom has been ionised and recombines with a free electron. The ionising radiation itself (also called Lyman continuum emission) which is needed for this process inside the LAEs could also be responsible for ionising the IGM around those galaxies at the epoch of reionisation, given that enough Lyman continuum escapes. Through this mechanism, Lyman alpha and Lyman continuum radiation are closely linked and are both studied to better understand the properties of high redshift galaxies and the reionisation state of the universe.
Before I can analyse their Lyman alpha emission lines and the escape of Lyman continuum emission from them, the first step is the detection and correct classification of LAEs in integral field spectroscopic data, specifically taken with the Multi-Unit Spectroscopic Explorer (MUSE). After detecting emission line objects in the MUSE data, the task of classifying them and determining their redshift is performed with the graphical user interface QtClassify, which I developed during the work on this thesis. It uses the strength of the combination of spectroscopic and photometric information that integral field spectroscopy offers to enable the user to quickly identify the nature of the detected emission lines. The reliable classification of LAEs and determination of their redshifts is a crucial first step towards an analysis of their properties.
Through radiative transfer processes, the properties of the neutral hydrogen clouds in and around LAEs are imprinted on the shape of the Lyman alpha line. Thus after identifying the LAEs in the MUSE data, I analyse the properties of the Lyman alpha emission line, such as the equivalent width (EW) distribution, the asymmetry and width of the line as well as the double peak fraction. I challenge the common method of displaying EW distributions as histograms without taking the limits of the survey into account and construct a more independent EW distribution function that better reflects the properties of the underlying population of galaxies. I illustrate this by comparing the fraction of high EW objects between the two surveys MUSE-Wide and MUSE-Deep, both consisting of MUSE pointings (each with the size of one square arcminute) of different depths. In the 60 MUSE-Wide fields of one hour exposure time I find a fraction of objects with extreme EWs above EW_0>240A of ~20%, while in the MUSE-Deep fields (9 fields with an exposure time of 10 hours and one with an exposure time of 31 hours) I find a fraction of only ~1%, which is due to the differences in the limiting line flux of the surveys. The highest EW I measure is EW_0 = 600.63 +- 110A, which hints at an unusual underlying stellar population, possibly with a very low metallicity.
With the knowledge of the redshifts and positions of the LAEs detected in the MUSE-Wide survey, I also look for Lyman continuum emission coming from these galaxies and analyse the connection between Lyman continuum emission and Lyman alpha emission. I use ancillary Hubble Space Telescope (HST) broadband photometry in the bands that contain the Lyman continuum and find six Lyman continuum leaker candidates. To test whether the Lyman continuum emission of LAEs is coming only from those individual objects or the whole population, I select LAEs that are most promising for the detection of Lyman continuum emission, based on their rest-frame UV continuum and Lyman alpha line shape properties. After this selection, I stack the broadband data of the resulting sample and detect a signal in Lyman continuum with a significance of S/N = 5.5, pointing towards a Lyman continuum escape fraction of ~80%. If the signal is reliable, it strongly favours LAEs as the providers of the hydrogen ionising emission at the epoch of reionisation and beyond.
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.
Thermoresponsive Zellkultursubstrate für zeitlich-räumlich gesteuertes Auswachsen neuronaler Zellen
(2019)
Ein wichtiges Ziel der Neurowissenschaften ist das Verständnis der komplexen und zugleich faszinierenden, hochgeordneten Vernetzung der Neurone im Gehirn, welche neuronalen Prozessen, wie zum Beispiel dem Wahrnehmen oder Lernen wie auch Neuropathologien zu Grunde liegt. Für verbesserte neuronale Zellkulturmodelle zur detaillierten Untersuchung dieser Prozesse ist daher die Rekonstruktion von geordneten neuronalen Verbindungen dringend erforderlich. Mit Oberflächenstrukturen aus zellattraktiven und zellabweisenden Beschichtungen können neuronale Zellen und ihre Neuriten in vitro strukturiert werden. Zur Kontrolle der neuronalen Verbindungsrichtung muss das Auswachsen der Axone zu benachbarten Zellen dynamisch gesteuert werden, zum Beispiel über eine veränderliche Zugänglichkeit der Oberfläche.
In dieser Arbeit wurde untersucht, ob mit thermoresponsiven Polymeren (TRP) beschichtete Zellkultursubstrate für eine dynamische Kontrolle des Auswachsens neuronaler Zellen geeignet sind. TRP können über die Temperatur von einem zellabweisenden in einen zellattraktiven Zustand geschaltet werden, womit die Zugänglichkeit der Oberfläche für Zellen dynamisch gesteuert werden kann. Die TRP-Beschichtung wurde mikrostrukturiert, um einzelne oder wenige neuronale Zellen zunächst auf der Oberfläche anzuordnen und das Auswachsen der Zellen und Neuriten über definierte TRP-Bereiche in Abhängigkeit der Temperatur zeitlich und räumlich zu kontrollieren. Das Protokoll wurde mit der neuronalen Zelllinie SH-SY5Y etabliert und auf humane induzierte Neurone übertragen. Die Anordnung der Zellen konnte bei Kultivierung im zellabweisenden Zustand des TRPs für bis zu 7 Tage aufrecht erhalten werden. Durch Schalten des TRPs in den zellattraktiven Zustand konnte das Auswachsen der Neuriten und Zellen zeitlich und räumlich induziert werden. Immunozytochemische Färbungen und Patch-Clamp-Ableitungen der Neurone demonstrierten die einfache Anwendbarkeit und Zellkompatibilität der TRP-Substrate.
Eine präzisere räumliche Kontrolle des Auswachsens der Zellen sollte durch lokales Schalten der TRP-Beschichtung erreicht werden. Dafür wurden Mikroheizchips mit Mikroelektroden zur lokalen Jouleschen Erwärmung der Substratoberfläche entwickelt. Zur Evaluierung der generierten Temperaturprofile wurde eine Temperaturmessmethode entwickelt und die erhobenen Messwerte mit numerisch simulierten Werten abgeglichen. Die Temperaturmessmethode basiert auf einfach zu applizierenden Sol-Gel-Schichten, die den temperatursensitiven Fluoreszenzfarbstoff Rhodamin B enthalten. Sie ermöglicht oberflächennahe Temperaturmessungen in trockener und wässriger Umgebung mit hoher Orts- und Temperaturauflösung. Numerische Simulationen der Temperaturprofile korrelierten gut mit den experimentellen Daten. Auf dieser Basis konnten Geometrie und Material der Mikroelektroden hinsichtlich einer lokal stark begrenzten Temperierung optimiert werden. Ferner wurden für die Kultvierung der Zellen auf den Mikroheizchips eine Zellkulturkammer und Kontaktboard für die elektrische Kontaktierung der Mikroelektroden geschaffen.
Die vorgestellten Ergebnisse demonstrieren erstmalig das enorme Potential thermoresponsiver Zellkultursubstrate für die zeitlich und räumlich gesteuerte Formation geordneter neuronaler Verbindungen in vitro. Zukünftig könnte dies detaillierte Studien zur neuronalen Informationsverarbeitung oder zu Neuropathologien an relevanten, humanen Zellmodellen ermöglichen.
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.
Emotions are a central element of human experience. They occur with high frequency in everyday life and play an important role in decision making. However, currently there is no consensus among researchers on what constitutes an emotion and on how emotions should be investigated. This dissertation identifies three problems of current emotion research: the problem of ground truth, the problem of incomplete constructs and the problem of optimal representation. I argue for a focus on the detailed measurement of emotion manifestations with computer-aided methods to solve these problems. This approach is demonstrated in three research projects, which describe the development of methods specific to these problems as well as their application to concrete research questions.
The problem of ground truth describes the practice to presuppose a certain structure of emotions as the a priori ground truth. This determines the range of emotion descriptions and sets a standard for the correct assignment of these descriptions. The first project illustrates how this problem can be circumvented with a multidimensional emotion perception paradigm which stands in contrast to the emotion recognition paradigm typically employed in emotion research. This paradigm allows to calculate an objective difficulty measure and to collect subjective difficulty ratings for the perception of emotional stimuli. Moreover, it enables the use of an arbitrary number of emotion stimuli categories as compared to the commonly used six basic emotion categories. Accordingly, we collected data from 441 participants using dynamic facial expression stimuli from 40 emotion categories. Our findings suggest an increase in emotion perception difficulty with increasing actor age and provide evidence to suggest that young adults, the elderly and men underestimate their emotion perception difficulty. While these effects were predicted from the literature, we also found unexpected and novel results. In particular, the increased difficulty on the objective difficulty measure for female actors and observers stood in contrast to reported findings. Exploratory analyses revealed low relevance of person-specific variables for the prediction of emotion perception difficulty, but highlighted the importance of a general pleasure dimension for the ease of emotion perception.
The second project targets the problem of incomplete constructs which relates to vaguely defined psychological constructs on emotion with insufficient ties to tangible manifestations. The project exemplifies how a modern data collection method such as face tracking data can be used to sharpen these constructs on the example of arousal, a long-standing but fuzzy construct in emotion research. It describes how measures of distance, speed and magnitude of acceleration can be computed from face tracking data and investigates their intercorrelations. We find moderate to strong correlations among all measures of static information on one hand and all measures of dynamic information on the other. The project then investigates how self-rated arousal is tied to these measures in 401 neurotypical individuals and 19 individuals with autism. Distance to the neutral face was predictive of arousal ratings in both groups. Lower mean arousal ratings were found for the autistic group, but no difference in correlation of the measures and arousal ratings could be found between groups. Results were replicated in a high autistic traits group consisting of 41 participants. The findings suggest a qualitatively similar perception of arousal for individuals with and without autism. No correlations between valence ratings and any of the measures could be found which emphasizes the specificity of our tested measures for the construct of arousal.
The problem of optimal representation refers to the search for the best representation of emotions and the assumption that there is a one-fits-all solution. In the third project we introduce partial least squares analysis as a general method to find an optimal representation to relate two high-dimensional data sets to each other. The project demonstrates its applicability to emotion research on the question of emotion perception differences between men and women. The method was used with emotion rating data from 441 participants and face tracking data computed on 306 videos. We found quantitative as well as qualitative differences in the perception of emotional facial expressions between these groups. We showed that women’s emotional perception systematically captured more of the variance in facial expressions. Additionally, we could show that significant differences exist in the way that women and men perceive some facial expressions which could be visualized as concrete facial expression sequences. These expressions suggest differing perceptions of masked and ambiguous facial expressions between the sexes. In order to facilitate use of the developed method by the research community, a package for the statistical environment R was written. Furthermore, to call attention to the method and its usefulness for emotion research, a website was designed that allows users to explore a model of emotion ratings and facial expression data in an interactive fashion.
Cette thèse d’urbanisme s’est donnée pour objectif de réfléchir à l’avenir des gares métropolitaines françaises et allemandes à horizon 2050. Elle porte une interrogation sur les fondements de la gare comme objet urbain conceptuel (abordé comme un système) et pose comme hypothèse qu’il serait en quelque sorte doté de propriétés autonomes. Parmi ces propriétés, c’est le processus d’expansion et de dialogue sans cesse renouvelé et conflictuel, entre la gare et son tissu urbain environnant, qui guide cette recherche ; notamment dans le rapport qu’il entretient avec l’hypermobilité des métropoles. Pour ce faire, cette thèse convoque quatre terrains d’études : les gares principales de Cologne et de Stuttgart en Allemagne et les gares de Paris-Montparnasse et Lyon-Part-Dieu en France ; et commence par un historique détaillé de leurs évolutions morphologiques, pour dégager une série de variables architectoniques et urbaines. Il procède dans un deuxième temps à une série d’analyse prospective, permettant de juger de l’influence possible des politiques publiques en matière transports et de mobilité, sur l’avenir conceptuel des gares. Cette thèse propose alors le concept de système-gare, pour décrire l’expansion et l’intégration des gares métropolitaines avec leur environnement urbain ; un processus de négociation dialectique qui ne trouve pas sa résolution dans le concept de gare comme lieu de vie/ville. Elle invite alors à penser la gare comme une hétérotopie, et propose une lecture dépolarisée et déhiérarchisée de ces espaces, en introduisant les concepts d’orchestre de gares et de métagare. Cette recherche propose enfin une lecture critique de la « ville numérique » et du concept de « mobilité comme service. » Pour éviter une mise en flux tendus potentiellement dommageables, l’application de ces concepts en gare ne pourra se soustraire à une augmentation simultanée des espaces physiques.
Im Rahmen dieser Dissertation konnten neue Kalium- und Natrium-Ionen Fluoreszenzfarbstoffe von der Klasse der Fluoroionophore synthetisiert und charakterisiert werden. Sie bestehen aus einem N Phenylazakronenether als Ionophor und unterschiedlichen Fluorophoren und sind über einen π-konjugierten 1,2,3-Triazol-1,4-diyl Spacer verbunden. Dabei lag der Fokus während ihrer Entwicklung darauf, diese in ihrer Sensitivität, Selektivität und in ihren photophysikalischen Eigenschaften so zu funktionalisieren, dass sie für intra- bzw. extrazelluläre Konzentrationsbestimmungen geeignet sind.
Durch Variation der in ortho Position der N-Phenylazakronenether befindlichen Alkoxy-Gruppen und der fluorophoren Gruppe der Fluoroionophore konnte festgestellt werden, dass die Sensitivität und Selektivität für Kalium- bzw. Natrium-Ionen jeweils durch eine bestimmte Isomerie der 1,2,3-Triazol-1,4-diyl-Einheit erhöht wird. Des Weiteren wurde gezeigt, dass durch eine erhöhte Einschränkung der N,N-Diethylamino-Gruppe des Fluorophors eine Steigerung der Fluoreszenzquantenausbeute und eine Verschiebung des Emissionsmaximums auf über 500 nm erreicht werden konnte. Die Einführung einer Isopropoxy-Gruppe an einem N-Phenylaza-[18]krone-6-ethers resultierte dabei in einem hoch selektiven Kalium-Ionen Fluoroionophor und ermöglichte eine in vitro Überwachung von 10 – 80 mM Kalium-Ionen. Die Substitution einer Methoxy-Gruppe an einem N-Phenylaza-[15]krone-5-ether kombiniert mit unterschiedlich N,N-Diethylamino-Coumarinen lieferte hingegen zwei Natrium-Ionen Fluoroionophore, die für die Überwachung von intra- bzw. extrazellulären Natrium-Ionen Konzentrationen geeignet sind.
In einem weiteren Schritt wurden N-Phenylaza-[18]krone-6-ether mit einem Fluorophor, basierend auf einem [1,3]-Dioxolo[4,5-f][1,3]benzodioxol-(DBD)-Grundgerüst, funktionalisiert. Die im Anschluss durchgeführten spektroskopischen Untersuchungen ergaben, dass die Isopropoxy-Gruppe in ortho Position des N-Phenylaza-[18]krone-6-ether in einen für extrazelluläre Kalium-Ionen Konzentrationen selektiven Fluoroionophor resultierte, der die Konzentrationsbestimmungen über die Fluoreszenzintensität und -lebensdauer ermöglicht.
In einem abschließenden Schritt konnte unter Verwendung eines Pyrens als fluorophore Gruppe ein weiterer für extrazelluläre Kalium-Ionen Konzentrationen geeigneter Fluoroionophor entwickelt werden. Die Bestimmung der Kalium-Ionen Konzentration erfolgte hierbei anhand der Fluoreszenzintensitätsverhältnisse bei zwei Emissionswellenlängen.
Insgesamt konnten 17 verschiedene neue Fluoroionophore für die Bestimmung von Kalium- bzw. Natrium-Ionen synthetisiert und charakterisiert werden. Sechs dieser neuen Moleküle ermöglichen in vitro Messungen der intra- oder extrazellulären Kalium- und Natrium-Ionen Konzentrationen und könnten zukünftig für in vivo Konzentrationsmessungen verwendet werden.
Kosmologie beschreibt die Entwicklung des Universums als Ganzes. Kosmologische Entdeckungen in Theorie und Praxis haben daher unser modernes wissenschaftliches Weltbild entscheidend geprägt. Die Vermittlung eines modernen Weltbildes durch Unterricht ist ein häufiger Wunsch in der naturwissenschaftlichen Bildungsdiskussion. Dennoch existieren weiterhin Forschungs- und Entwicklungsbedarfe. Kosmologische Themen finden sich häufig in den Medien und sind gleichzeitig weiter vom Alltag entfernt, so dass sich hier besonders leicht wissenschaftlich inkorrekte Vorstellungen entwickeln können, die zu Problemen im Unterricht führen können.
Das Ziel dieser wissenschaftlichen Arbeit ist es, zu diesem Forschungsgebiet beizutragen und die Voraussetzungen hinsichtlich vorhandener Vorkenntnisse und Präkonzepte in Kosmologie, mit denen Schülerinnen und Schüler in den Unterricht kommen, zu untersuchen und anschließend mit denen anderer Länder zu vergleichen. Dies erfolgt anhand einer qualitativen Inhaltsanalyse eines offenen Fragebogens. Auf dieser Grundlage wird schließlich ein Multiple-Choice Fragebogen entwickelt, angewendet und evaluiert.
Die Ergebnisse zeigen große Wissenslücken im Bereich der Kosmologie auf und geben erste Hinweise auf vorhandene Unterschiede zwischen den Ländern. Es existieren ebenfalls einige teils weit verbreitete wissenschaftlich inkorrekte Vorstellungen wie beispielsweise die Assoziation des Urknalls mit einer Explosion, der Urknall verursacht durch eine Kollision von Teilchen oder größeren Objekten, oder die Vorstellung der Ausdehnung des Universums als neue Entdeckungen und/oder Wissen. Des Weiteren gab nur etwa jeder Fünfte das korrekte Alter des Universums oder die Ausdehnung des Universums als einen der drei Belege der Urknalltheorie an, während fast 40% keinen einzigen Beleg nennen konnten. Für den geschlossenen Fragebogen konnten gute Hinweise für verschiedene Validitätsaspekte herausgearbeitet werden und es existieren erste Hinweise darauf, dass der Fragebogen Wissenszuwachs messen kann und damit wahrscheinlich zur Untersuchung der Wirksamkeit von Lerneinheiten eingesetzt werden kann. Auch ein entsprechendes Modell zur Verständnisentwicklung der Ausdehnung des Universums zeigte sich vielversprechend.
Diese Arbeit liefert insgesamt einen Forschungsbeitrag zum Schülervorwissen und Vorstellungen in der Kosmologie und deren Large Scale Assessment. Dies eröffnet die Möglichkeit zukünftiger Forschungen im Bereich von Gruppenvergleichen insbesondere hinsichtlich objektiver Ländervergleiche sowie der Untersuchungen der Wirksamkeit von einzelnen Lerneinheiten als auch Vergleiche verschiedener Lerneinheiten untereinander.
The main goal of this thesis is to explore the feasibility of using cross-lingual annotation projection as a method of alleviating the task of manual coreference annotation.
To reach our goal, we build a first trilingual parallel coreference corpus that encompasses multiple genres. For the annotation of the corpus, we develop common coreference annotation guidelines that are applicable to three languages (English, German, Russian) and include a novel domain-independent typology of bridging relations as well as state-of-the-art near-identity categories.
Thereafter, we design and perform several annotation projection experiments. In the first experiment, we implement a direct projection method with only one source language. Our results indicate that, already in a knowledge-lean scenario, our projection approach is superior to the most closely related work of Postolache et al. (2006). Since the quality of the resulting annotations is to a high degree dependent on the word alignment, we demonstrate how using limited syntactic information helps to further improve mention extraction on the target side. As a next step, in our second experiment, we show how exploiting two source languages helps to improve the quality of target annotations for both language pairs by concatenating annotations projected from two source languages. Finally, we assess the projection quality in a fully automatic scenario (using automatically produced source annotations), and propose a pilot experiment on manual projection of bridging pairs.
For each of the experiments, we carry out an in-depth error analysis, and we conclude that noisy word alignments, translation divergences and morphological and syntactic differences between languages are responsible for projection errors. We systematically compare and evaluate our projection methods, and we investigate the errors both qualitatively and quantitatively in order to identify problematic cases. Finally, we discuss the applicability of our method to coreference annotations and propose several avenues of future research.
This dissertation investigates the impact of the economic and fiscal crisis starting in 2008 on EU climate policy-making. While the overall number of adopted greenhouse gas emission reduction policies declined in the crisis aftermath, EU lawmakers decided to introduce new or tighten existing regulations in some important policy domains. Existing knowledge about the crisis impact on EU legislative decision-making cannot explain these inconsistencies. In response, this study develops an actor-centred conceptual framework based on rational choice institutionalism that provides a micro-level link to explain how economic crises translate into altered policy-making patterns. The core theoretical argument draws on redistributive conflicts, arguing that tensions between ‘beneficiaries’ and ‘losers’ of a regulatory initiative intensify during economic crises and spill over to the policy domain. To test this hypothesis and using social network analysis, this study analyses policy processes in three case studies: The introduction of carbon dioxide emission limits for passenger cars, the expansion of the EU Emissions Trading System to aviation, and the introduction of a regulatory framework for biofuels. The key finding is that an economic shock causes EU policy domains to polarise politically, resulting in intensified conflict and more difficult decision-making. The results also show that this process of political polarisation roots in the industry that is the subject of the regulation, and that intergovernmental bargaining among member states becomes more important, but also more difficult in times of crisis.
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.
Additive Manufacturing (AM) in terms of laser powder-bed fusion (L-PBF) offers new prospects regarding the design of parts and enables therefore the production of lattice structures. These lattice structures shall be implemented in various industrial applications (e.g. gas turbines) for reasons of material savings or cooling channels. However, internal defects, residual stress, and structural deviations from the nominal geometry are unavoidable.
In this work, the structural integrity of lattice structures manufactured by means of L-PBF was non-destructively investigated on a multiscale approach.
A workflow for quantitative 3D powder analysis in terms of particle size, particle shape, particle porosity, inter-particle distance and packing density was established. Synchrotron computed tomography (CT) was used to correlate the packing density with the particle size and particle shape. It was also observed that at least about 50% of the powder porosity was released during production of the struts.
Struts are the component of lattice structures and were investigated by means of laboratory CT. The focus was on the influence of the build angle on part porosity and surface quality. The surface topography analysis was advanced by the quantitative characterisation of re-entrant surface features. This characterisation was compared with conventional surface parameters showing their complementary information, but also the need for AM specific surface parameters.
The mechanical behaviour of the lattice structure was investigated with in-situ CT under compression and successive digital volume correlation (DVC). The deformation was found to be knot-dominated, and therefore the lattice folds unit cell layer wise.
The residual stress was determined experimentally for the first time in such lattice structures. Neutron diffraction was used for the non-destructive 3D stress investigation. The principal stress directions and values were determined in dependence of the number of measured directions. While a significant uni-axial stress state was found in the strut, a more hydrostatic stress state was found in the knot. In both cases, strut and knot, seven directions were at least needed to find reliable principal stress directions.
Supercapacitors are electrochemical energy storage devices with rapid charge/discharge rate and long cycle life. Their biggest challenge is the inferior energy density compared to other electrochemical energy storage devices such as batteries. Being the most widely spread type of supercapacitors, electrochemical double-layer capacitors (EDLCs) store energy by electrosorption of electrolyte ions on the surface of charged electrodes. As a more recent development, Na-ion capacitors (NICs) are expected to be a more promising tactic to tackle the inferior energy density due to their higher-capacity electrodes and larger operating voltage. The charges are simultaneously stored by ion adsorption on the capacitive-type cathode surface and via faradic process in the battery-type anode, respectively. Porous carbon electrodes are of great importance in these devices, but the paramount problems are the facile synthetic routes for high-performance carbons and the lack of fundamental understanding of the energy storage mechanisms. Therefore, the aim of the present dissertation is to develop novel synthetic methods for (nitrogen-doped) porous carbon materials with superior performance, and to reveal a deeper understanding energy storage mechanisms of EDLCs and NICs.
The first part introduces a novel synthetic method towards hierarchical ordered meso-microporous carbon electrode materials for EDLCs. The large amount of micropores and highly ordered mesopores endow abundant sites for charge storage and efficient electrolyte transport, respectively, giving rise to superior EDLC performance in different electrolytes. More importantly, the controversial energy storage mechanism of EDLCs employing ionic liquid (IL) electrolytes is investigated by employing a series of porous model carbons as electrodes. The results not only allow to conclude on the relations between the porosity and ion transport dynamics, but also deliver deeper insights into the energy storage mechanism of IL-based EDLCs which is different from the one usually dominating in solvent-based electrolytes leading to compression double-layers.
The other part focuses on anodes of NICs, where novel synthesis of nitrogen-rich porous carbon electrodes and their sodium storage mechanism are investigated. Free-standing fibrous nitrogen-doped carbon materials are synthesized by electrospinning using the nitrogen-rich monomer (hexaazatriphenylene-hexacarbonitrile, C18N12) as the precursor followed by condensation at high temperature. These fibers provide superior capacity and desirable charge/discharge rate for sodium storage. This work also allows insights into the sodium storage mechanism in nitrogen-doped carbons. Based on this mechanism, further optimization is done by designing a composite material composed of nitrogen-rich carbon nanoparticles embedded in conductive carbon matrix for a better charge/discharge rate. The energy density of the assembled NICs significantly prevails that of common EDLCs while maintaining the high power density and long cycle life.
Due to its bioavailability and (bio)degradability, poly(lactide) (PLA) is an interesting polymer that is already being used as packaging material, surgical seam, and drug delivery system. Dependent on various parameters such as polymer composition, amphiphilicity, sample preparation, and the enantiomeric purity of lactide, PLA in an amphiphilic block copolymer can affect the self-assembly behavior dramatically. However, sizes and shapes of aggregates have a critical effect on the interactions between biological and drug delivery systems, where the general understanding of these polymers and their ability to influence self-assembly is of significant interest in science.
The first part of this thesis describes the synthesis and study of a series of linear poly(L-lactide) (PLLA) and poly(D-lactide) (PDLA)-based amphiphilic block copolymers with varying PLA (hydrophobic), and poly(ethylene glycol) (PEG) (hydrophilic) chain lengths and different block copolymer sequences (PEG-PLA and PLA-PEG). The PEG-PLA block copolymers were synthesized by ring-opening polymerization of lactide initiated by a PEG-OH macroinitiator. In contrast, the PLA-PEG block copolymers were produced by a Steglich-esterification of modified PLA with PEG-OH.
The aqueous self-assembly at room temperature of the enantiomerically pure PLLA-based block copolymers and their stereocomplexed mixtures was investigated by dynamic light scattering (DLS), transmission electron microscopy (TEM), wide-angle X-ray diffraction (WAXD), and differential scanning calorimetry (DSC). Spherical micelles and worm-like structures were produced, whereby the obtained self-assembled morphologies were affected by the lactide weight fraction in the block copolymer and self-assembly time. The formation of worm-like structures increases with decreasing PLA-chain length and arises from spherical micelles, which become colloidally unstable and undergo an epitaxial fusion with other micelles. As shown by DSC experiments, the crystallinity of the corresponding PLA blocks increases within the self-assembly time. However, the stereocomplexed self-assembled structures behave differently from the parent polymers and result in irregular-shaped clusters of spherical micelles. Additionally, time-dependent self-assembly experiments showed a transformation, from already self-assembled morphologies of different shapes to more compact micelles upon stereocomplexation.
In the second part of this thesis, with the objective to influence the self-assembly of PLA-based block copolymers and its stereocomplexes, poly(methyl phosphonate) (PMeP) and poly(isopropyl phosphonate) (PiPrP) were produced by ring-opening polymerization to implement an alternative to the hydrophilic block PEG. Although, the 1,8 diazabicyclo[5.4.0]unde 7 ene (DBU) or 1,5,7 triazabicyclo[4.4.0]dec-5-ene (TBD) mediated synthesis of the corresponding poly(alkyl phosphonate)s was successful, however, not so the polymerization of copolymers with PLA-based precursors (PLA-homo polymers, and PEG-PLA block copolymers). Transesterification, obtained by 1H-NMR spectroscopy, between the poly(phosphonate)- and PLA block caused a high-field shifted peak split of the methine proton in the PLA polymer chain, with split intensities depending on the used catalyst (DBU for PMeP, and TBD for PiPrP polymerization). An additional prepared block copolymer PiPrP-PLLA that wasn’t affected in its polymer sequence was finally used for self-assembly experiments with PLA-PEG and PEG-PLA mixing.
This work provides a comprehensive study of the self-assembly behavior of PLA-based block copolymers influenced by various parameters such as polymer block lengths, self-assembly time, and stereocomplexation of block copolymer mixtures.
The central motivation of the thesis was to provide possible solutions and concepts to improve the performance (e.g. activity and selectivity) of electrochemical N2 reduction reaction (NRR). Given that porous carbon-based materials usually exhibit a broad range of structural properties, they could be promising NRR catalysts. Therefore, the advanced design of novel porous carbon-based materials and the investigation of their application in electrocatalytic NRR including the particular reaction mechanisms are the most crucial points to be addressed. In this regard, three main topics were investigated. All of them are related to the functionalization of porous carbon for electrochemical NRR or other electrocatalytic reactions.
In chapter 3, a novel C-TixOy/C nanocomposite has been described that has been obtained via simple pyrolysis of MIL-125(Ti). A novel mode for N2 activation is achieved by doping carbon atoms from nearby porous carbon into the anion lattice of TixOy. By comparing the NRR performance of M-Ts and by carrying out DFT calculations, it is found that the existence of (O-)Ti-C bonds in C-doped TixOy can largely improve the ability to activate and reduce N2 as compared to unoccupied OVs in TiO2. The strategy of rationally doping heteroatoms into the anion lattice of transition metal oxides to create active centers may open many new opportunities beyond the use of noble metal-based catalysts also for other reactions that require the activation of small molecules as well.
In chapter 4, a novel catalyst construction composed of Au single atoms decorated on the surface of NDPCs was reported. The introduction of Au single atoms leads to active reaction sites, which are stabilized by the N species present in NDPCs. Thus, the interaction within as-prepared AuSAs-NDPCs catalysts enabled promising performance for electrochemical NRR. For the reaction mechanism, Au single sites and N or C species can act as Frustrated Lewis pairs (FLPs) to enhance the electron donation and back-donation process to activate N2 molecules. This work provides new opportunities for catalyst design in order to achieve efficient N2 fixation at ambient conditions by utilizing recycled electric energy.
The last topic described in chapter 5 mainly focused on the synthesis of dual heteroatom-doped porous carbon from simple precursors. The introduction of N and B heteroatoms leads to the construction of N-B motives and Frustrated Lewis pairs in a microporous architecture which is also rich in point defects. This can improve the strength of adsorption of different reactants (N2 and HMF) and thus their activation. As a result, BNC-2 exhibits a desirable electrochemical NRR and HMF oxidation performance. Gas adsorption experiments have been used as a simple tool to elucidate the relationship between the structure and catalytic activity. This work provides novel and deep insights into the rational design and the origin of activity in metal-free electrocatalysts and enables a physically viable discussion of the active motives, as well as the search for their further applications.
Throughout this thesis, the ubiquitous problems of low selectivity and activity of electrochemical NRR are tackled by designing porous carbon-based catalysts with high efficiency and exploring their catalytic mechanisms. The structure-performance relationships and mechanisms of activation of the relatively inert N2 molecules are revealed by either experimental results or DFT calculations. These fundamental understandings pave way for a future optimal design and targeted promotion of NRR catalysts with porous carbon-based structure, as well as study of new N2 activation modes.
Objeto de esta investigación es el auge y caída de una legitimación teológica de la poesía que tuvo lugar en el virreinato del Perú entre fines del siglo XVI y la segunda mitad del siglo XVII. Su punto cúlmine está marcado por el surgimiento de una “Academia Antártica” en las primeras décadas del siglo XVII, mientras que su fin, se aprecia a fines del mismo siglo, cuando eruditos de las órdenes religiosas, especialmente Juan de Espinosa y Medrano en sus textos en defensa de la poesía y las ciencias, negaron a la poesía cualquier estatuto teológico, sirviéndose sin embargo de ella para escribir sus sermones y textos. A partir del auge y caída de esta legitimación teológica en el virreinato del Perú, este estudio muestra la existencia de dos movimientos que forman un quiasmo entre una teologización de la poesía y una poetización de la teología, en cuyo centro velado se encuentra en disputa el saber teórico y práctico de la poesía. Lo que está en disputa en este sentido no es la poesía, entendida como una cumbre de las bellas letras, sino la posesión legítima de un modo de lectura analógico y tipológico del orden del universo, fundado en las Sagradas Escrituras y en la historia de la salvación, y un modo poético para doctrinar a todos los miembros de la sociedad virreinal en concordancia con aquel modo de lectura.