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In littoral zones of lakes, multiple processes determine lake ecology and water quality. Lacustrine groundwater discharge (LGD), most frequently taking place in littoral zones, can transport or mobilize nutrients from the sediments and thus contribute significantly to lake eutrophication. Furthermore, lake littoral zones are the habitat of benthic primary producers, namely submerged macrophytes and periphyton, which play a key role in lake food webs and influence lake water quality. Groundwater-mediated nutrient-influx can potentially affect the asymmetric competition between submerged macrophytes and periphyton for light and nutrients. While rooted macrophytes have superior access to sediment nutrients, periphyton can negatively affect macrophytes by shading. LGD may thus facilitate periphyton production at the expense of macrophyte production, although studies on this hypothesized effect are missing.
The research presented in this thesis is aimed at determining how LGD influences periphyton, macrophytes, and the interactions between these benthic producers. Laboratory experiments were combined with field experiments and measurements in an oligo-mesotrophic hard water lake.
In the first study, a general concept was developed based on a literature review of the existing knowledge regarding the potential effects of LGD on nutrients and inorganic and organic carbon loads to lakes, and the effect of these loads on periphyton and macrophytes. The second study includes a field survey and experiment examining the effects of LGD on periphyton in an oligotrophic, stratified hard water lake (Lake Stechlin). This study shows that LGD, by mobilizing phosphorus from the sediments, significantly promotes epiphyton growth, especially at the end of the summer season when epilimnetic phosphorus concentrations are low. The third study focuses on the potential effects of LGD on submerged macrophytes in Lake Stechlin. This study revealed that LGD may have contributed to an observed change in macrophyte community composition and abundance in the shallow littoral areas of the lake. Finally, a laboratory experiment was conducted which mimicked the conditions of a seepage lake. Groundwater circulation was shown to mobilize nutrients from the sediments, which significantly promoted periphyton growth. Macrophyte growth was negatively affected at high periphyton biomasses, confirming the initial hypothesis.
More generally, this thesis shows that groundwater flowing into nutrient-limited lakes may import or mobilize nutrients. These nutrients first promote periphyton, and subsequently provoke radical changes in macrophyte populations before finally having a possible influence on the lake’s trophic state. Hence, the eutrophying effect of groundwater is delayed and, at moderate nutrient loading rates, partly dampened by benthic primary producers. The present research emphasizes the importance and complexity of littoral processes, and the need to further investigate and monitor the benthic environment. As present and future global changes can significantly affect LGD, the understanding of these complex interactions is required for the sustainable management of lake water quality.
The Cauchy problem for the linearised Einstein equation and the Goursat problem for wave equations
(2017)
In this thesis, we study two initial value problems arising in general relativity. The first is the Cauchy problem for the linearised Einstein equation on general globally hyperbolic spacetimes, with smooth and distributional initial data. We extend well-known results by showing that given a solution to the linearised constraint equations of arbitrary real Sobolev regularity, there is a globally defined solution, which is unique up to addition of gauge solutions. Two solutions are considered equivalent if they differ by a gauge solution. Our main result is that the equivalence class of solutions depends continuously on the corre- sponding equivalence class of initial data. We also solve the linearised constraint equations in certain cases and show that there exist arbitrarily irregular (non-gauge) solutions to the linearised Einstein equation on Minkowski spacetime and Kasner spacetime.
In the second part, we study the Goursat problem (the characteristic Cauchy problem) for wave equations. We specify initial data on a smooth compact Cauchy horizon, which is a lightlike hypersurface. This problem has not been studied much, since it is an initial value problem on a non-globally hyperbolic spacetime. Our main result is that given a smooth function on a non-empty, smooth, compact, totally geodesic and non-degenerate Cauchy horizon and a so called admissible linear wave equation, there exists a unique solution that is defined on the globally hyperbolic region and restricts to the given function on the Cauchy horizon. Moreover, the solution depends continuously on the initial data. A linear wave equation is called admissible if the first order part satisfies a certain condition on the Cauchy horizon, for example if it vanishes. Interestingly, both existence of solution and uniqueness are false for general wave equations, as examples show. If we drop the non-degeneracy assumption, examples show that existence of solution fails even for the simplest wave equation. The proof requires precise energy estimates for the wave equation close to the Cauchy horizon. In case the Ricci curvature vanishes on the Cauchy horizon, we show that the energy estimates are strong enough to prove local existence and uniqueness for a class of non-linear wave equations. Our results apply in particular to the Taub-NUT spacetime and the Misner spacetime. It has recently been shown that compact Cauchy horizons in spacetimes satisfying the null energy condition are necessarily smooth and totally geodesic. Our results therefore apply if the spacetime satisfies the null energy condition and the Cauchy horizon is compact and non-degenerate.
The Bruce effect revisited
(2017)
Pregnancy termination after encountering a strange male, the Bruce effect, is regarded as a counterstrategy of female mammals towards anticipated infanticide. While confirmed in caged rodent pairs, no verification for the Bruce effect existed from experimental field populations of small rodents. We suggest that the effect may be adaptive for breeding rodent females only under specific conditions related to populations with cyclically fluctuating densities. We investigated the occurrence of delay in birth date after experimental turnover of the breeding male under different population composition in bank voles (Myodes glareolus) in large outdoor enclosures: one-male–multiple-females (n = 6 populations/18 females), multiple-males–multiple-females (n = 15/45), and single-male–single-female (MF treatment, n = 74/74). Most delays were observed in the MF treatment after turnover. Parallel we showed in a laboratory experiment (n = 205 females) that overwintered and primiparous females, the most abundant cohort during population lows in the increase phase of cyclic rodent populations, were more likely to delay births after turnover of the male than year-born and multiparous females. Taken together, our results suggest that the Bruce effect may be an adaptive breeding strategy for rodent females in cyclic populations specifically at low densities in the increase phase, when isolated, overwintered animals associate in MF pairs. During population lows infanticide risk and inbreeding risk may then be higher than during population highs, while also the fitness value of a litter in an increasing population is higher. Therefore, the Bruce effect may be adaptive for females during annual population lows in the increase phases, even at the costs of delaying reproduction.
Recent research has called into question the current practice to estimate individual usual food intake in large-scale studies. In such studies, usual food intake has been defined as diet over the past year. The aim of this review is to summarise the concepts of dietary assessment methods providing food intake data over this time period. A conceptualised framework is given to help researchers to understand the more recent developments to improve dietary assessment in large-scale prospective studies, and also to help to spot the gaps that need to be addressed in future methodological research. The conceptual framework illustrates the current options for the assessment of an individual’s food consumption over 1 year. Ideally, a person’s food intake on each day of this year should be assessed. Due to participants’ burden, and organisational and financial constraints, however, the options are limited to directly requesting the long-term average (e.g. food frequency questionnaires), or selecting a few days with detailed food consumption measurements (e.g. 24-hour dietary recalls) or using snapshot techniques (e.g. barcode scanning of purchases). It seems necessary and important to further evaluate the performance of statistical modelling of the individual usual food intake from all available sources. Future dietary assessment might profit from the growing prominence of internet and telecommunication technologies to further enhance the available data on food consumption for each study participant. Research is crucial to investigate the performance of innovative assessment tools. However, the self-reported nature of the data itself will always lead to bias.
This research was designed to adapt and investigate the psychometric properties of the Short Dark Triad measure (Jones and Paulhus Assessment, 21(1), 28-41, 2014) in a German sample within four studies (total N = 1463); the measure evaluates three personality dimensions: narcissism, psychopathy, and Machiavellianism. The structure of the instrument was analysed by Confirmatory Factor Analyses procedure. It indicated that the three-factor structure had the best fit to the data. Next, the Short Dark Triad measure was evaluated in terms of construct, convergent and discriminant validity, internal consistency (≥ .72), and test-retest reliability during a 4-week period (≥ .73). Concurrent validity of the SD3 was supported by relating its subscales to measures of the Big Five concept, aggression, and self-esteem. We concluded that the Short Dark Triad instrument presented high cross-language replicability. The use of this short inventory in the investigation of the Dark Triad personality model in the German language context is suggested.
Information on the contemporary in-situ stress state of the earth’s crust is essential for geotechnical applications and physics-based seismic hazard assessment. Yet, stress data records for a data point are incomplete and their availability is usually not dense enough to allow conclusive statements. This demands a thorough examination of the in-situ stress field which is achieved by 3D geomechanicalnumerical models. However, the models spatial resolution is limited and the resulting local stress state is subject to large uncertainties that confine the significance of the findings. In addition, temporal variations of the in-situ stress field are naturally or anthropogenically induced. In my thesis I address these challenges in three manuscripts that investigate (1) the current crustal stress field orientation, (2) the 3D geomechanical-numerical modelling of the in-situ stress state, and (3) the phenomenon of injection induced temporal stress tensor rotations. In the first manuscript I present the first comprehensive stress data compilation of Iceland with 495 data records. Therefore, I analysed image logs from 57 boreholes in Iceland for indicators of the orientation of the maximum horizontal stress component. The study is the first stress survey from different kinds of stress indicators in a geologically very young and tectonically active area of an onshore spreading ridge. It reveals a distinct stress field with a depth independent stress orientation even very close to the spreading centre. In the second manuscript I present a calibrated 3D geomechanical-numerical modelling approach of the in-situ stress state of the Bavarian Molasse Basin that investigates the regional (70x70x10km³) and local (10x10x10km³) stress state. To link these two models I develop a multi-stage modelling approach that provides a reliable and efficient method to derive from the larger scale model initial and boundary conditions for the smaller scale model. Furthermore, I quantify the uncertainties in the models results which are inherent to geomechanical-numerical modelling in general and the multi-stage approach in particular. I show that the significance of the models results is mainly reduced due to the uncertainties in the material properties and the low number of available stress magnitude data records for calibration. In the third manuscript I investigate the phenomenon of injection induced temporal stress tensor rotation and its controlling factors. I conduct a sensitivity study with a 3D generic thermo-hydro-mechanical model. I show that the key control factors for the stress tensor rotation are the permeability as the decisive factor, the injection rate, and the initial differential stress. In particular for enhanced geothermal systems with a low permeability large rotations of the stress tensor are indicated. According to these findings the estimation of the initial differential stress in a reservoir is possible provided the permeability is known and the angle of stress rotation is observed. I propose that the stress tensor rotations can be a key factor in terms of the potential for induced seismicity on pre-existing faults due to the reorientation of the stress field that changes the optimal orientation of faults.
Für den Industrialisierungsprozess von Entwicklungs- und Schwellenländern haben ausländische Direktinvestitionen (ADI) eine wichtige Funktion. Sie können zum einen zu einer Erhöhung des industriellen Output des Ziellandes führen und zum anderen als Träger von technologischem Wissen fungieren. Neues Wissen kann den Empfängerländern der ADI durch Spillovereffekte und Technologietransfers ausländischer Tochterunternehmen zufließen. Diese Arbeit soll Antworten auf die Fragen geben, durch welche Mechanismen Spillovereffekte und Technologietransfers ausgelöst werden und wie Entwicklungs- und Schwellenländern diesen Wissenszufluss zur Beschleunigung ihres Industrialisierungsprozesses einsetzen können. Hierfür wird ein Konzept zur Förderung von Spillovereffekten entwickelt. Weiterhin wird ein theoretisches Modell entwickelt, in dem der Technologietransfer ausländischer Exportplattformen erstmals in Abhängigkeit des Anteils der Vorprodukte, die im Gastland nachgefragt werden, untersucht. In den Fallstudien Irland und Malaysia werden die Ergebnisse des theoretischen Modells sowie des entwickelten Konzepts illustriert.
Der technologische Wandel stellt Organisationen vor die Herausforderung, Innovationen möglichst schnell produktiv zu nutzen und damit einen Wettbewerbsvorteil zu erzielen. Der Erfolg der Technologieeinführung hängt stark mit der Schaffung von Akzeptanz bei den Mitarbeitern zusammen. Bestehende Ansätze wie die Diffusionstheorie (Rogers, 2003) oder das Technology Acceptance Model (Davis, 1989; Venkatesh und Davis, 1996; Venkatesh und Davis, 2000; Venkatesh, Morris u. a., 2003) widmen sich dem Organisationskontext jedoch nur am Rande. Ihre Modelle zielen auf die Übernahme einer Technologie in freier Entscheidung und im Marktkontext ab. Weiterhin beleuchten sie den Widerstand gegen Neuerungen nicht, welcher sich bei der verpflichtenden Übernahme bilden kann. Zur Untersuchung der Technologieeinführung und von Akzeptanzbildungsprozessen in Organisationen sind sie daher nur begrenzt nutzbar.
Das Ziel dieser Arbeit ist es daher, den spezifischen Einfluss des Kontextes Organisation auf die Akzeptanz und das Nutzungsverhalten herauszuarbeiten. Konkreter soll die Forschungsfrage geklärt werden, welchen Einfluss unterschiedliche Organisationstypen auf die Akzeptanz- und Nutzungsdynamik innerhalb von Organisationen haben. Hierfür wird die Erweiterung und Synthese bestehender Modelle der Akzeptanzforschung um organisationsspezifische Attribute vorgenommen. Das resultierende Modell erfasst die dynamische Entwicklung innerhalb der Organisation und ermöglicht damit die Beobachtung des Wandels. Die Funktionsweise des entwickelten Modells soll in einem Simulationsexperiment demonstriert und die Wirkung unterschiedlicher Organisationsformen verdeutlicht werden.
Das Modell vereint daher zwei Perspektiven: Die personale Perspektive fasst Akzeptanz als kognitiv-psychischen Prozess auf individueller Ebene. Dieser basiert auf den Kalkülen und Entscheidungen einzelner Personen. Zentral sind hierfür die Beiträge der Diffusionstheorie (Rogers, 2003) sowie das Technology Acceptance Model in seinen diversen Weiterentwicklungen und Veränderungen (Davis, 1989; Venkatesh und Davis, 1996; Venkatesh und Davis, 2000; Venkatesh, Morris u. a., 2003). Individuelle Faktoren aus unterschiedlichen Fit-Theorien (Goodhue und Thompson, 1995; Floyd, 1986; Liu, Lee und Chen, 2011; Parkes, 2013) werden genutzt, um diese Modelle anzureichern. Neben der Entwicklung
einer positiven, förderlichen Einstellung muss jedoch auch die Ablehnung und das offene Opponieren gegen die Innovation berücksichtigt werden (Patsiotis, Hughes und Webber, 2012).
Die organisatorische Perspektive hingegen sieht Akzeptanzentscheidungen eingebettet in den sozialen Kontext der Organisation. Die gegenseitige Beeinflussung basiert auf der Beobachtung der Umgebung und der Internalisierung sozialen Drucks. Dem steht in Organisationen die intendierte Beeinflussung in Form von Steuerung gegenüber. Beide Vorgänge formen das Akzeptanz- oder das Nutzungsverhalten der Mitarbeiter. Ausgehend von einem systemtheoretischen Organisationsbegriff werden unterschiedliche Steuerungsmedien (Luhmann, 1997; Fischer, 2009) vorgestellt. Diese können durch Steuerungsakteure
(Change Agents, Management) intendiert eingesetzt werden, um den Akzeptanz- und Nutzungsprozess über Interventionen zu gestalten.
Die Wirkung der Medien unterscheidet sich in verschiedenen Organisationstypen. Zur Analyse unterschiedlicher Organisationstypen werden die Konfigurationen nach Mintzberg (1979) herangezogen. Diese zeichnen sich durch unterschiedliche Koordinationsmechanismen aus, welche wiederum auf dem Einsatz von Steuerungsmedien beruhen.
Die Demonstration der Funktionsweise und Analysemöglichkeiten des entwickelten Modells erfolgt anhand eines Simulationsexperiments mittels der Simulationsplattform AnyLogic. Das Gültigkeitsspektrum wird anhand einer Sensitivitätsanalyse geprüft.
In der Simulation lassen sich spezifische Muster der Nutzung und Akzeptanzentwicklung nachweisen. Die Akzeptanz ist durch ein initiales Absinken und ein anschließendes gedämpftes Wachstum gekennzeichnet. Die Nutzung wird in der Organisation hingegen schnell durchgesetzt und verharrt dann auf einem stabilen Niveau. Für die Organisationstypen konnten unterschiedliche Effekte beobachtet werden. So eignet sich die bürokratische Steuerungsform zur Nutzungserhöhung, schafft es jedoch nicht, die Akzeptanz zu steigern. Organisationen, welche eher auf gegenseitige Abstimmung zur Koordination ausgelegt sind, erhöhen die Akzeptanz, jedoch nicht die Nutzung. Weiterhin ist die Entwicklung der Akzeptanz in diesem Organisationstyp sehr unsicher und weist einen hohen Schwankungsbereich auf.
In Zeiten eines sich schnell ändernden und vielseitigen Energiemarktes müssen Kohlenstoffmaterialien für verschiedene Anforderungen einsetzbar sein. Dies erfordert flexibel synthetisierbare Kohlenstoffmaterialien bevorzugt aus günstigen und nachhaltigen Kohlenstoffquellen. Es ist allerdings nicht leicht Vorläuferverbindungen auszumachen, welche sich einerseits für verschiedene Herstellungsverfahren eignen und deren Kohlenstoffprodukte andererseits in spezifischen Eigenschaften, wie der Struktur, des Stickstoffanteils, der Oberfläche und der Porengrößen, eingestellt werden können. In diesem Zusammenhang können natürliche Polyphenole, etwa überschüssige Tannine aus der Weinproduktion, eine neue Welt zu hoch funktionalen und vielseitig einstellbaren Kohlenstoffmaterialien mit hohen Ausbeuten öffnen.
Das Hauptziel dieser vorliegenden Thesis war es neue funktionale, einstellbare und skalierbare nanostrukturierte Kohlenstoffmaterialien aus Tanninen (insbesondere Tanninsäure) für unterschiedliche elektrochemische Zwecke zu synthetisieren und zu charakterisieren. Ermöglicht wurde dies durch unterschiedliche synthetische Herangehensweisen, wie etwa der polymeren Strukturdirektion, dem ionothermalen Templatieren und der weichen Templatierung. An Stelle des weitläufig gebräuchlichen, aber kanzerogenen Vernetzungsagens Formaldehyd wurden bei den vorgestellten Synthesen Harnstoff und Thioharnstoff gewählt, um zugleich die synthetisierten Kohlenmaterialien variabel dotieren zu können.
Daher wurden im ersten Teil der Arbeit die Wechselwirkungen, Reaktionen und thermischen Verhaltensweisen von Tanninsäure und Mixturen von Tanninsäure und Harnstoff bzw. Thioharnstoff untersucht, um daraus wichtige Erkenntnisse für die verschiedenen Kohlenstoffsynthesen zu gewinnen.
Durch die Verwendung eines polymeren Strukturierungsagenz Pluronic P123 konnten in einer ersten Kohlenstoffsynthese nachhaltige und dotierbare Kohlenstoffpartikel mit Durchmessern im Nanometerbereich aus Tanninsäure und Harnstoff hergestellt werden. Es konnte dabei gezeigt werden, dass durch die Modifikation der verschiedenen Syntheseparameter die Kohlenstoffnanopartikel gemäß ihres gemittelten Partikeldurchmessers, ihrer BET-Oberfläche, ihrer Komposition, ihrer Leitfähigkeit und ihrer chemischen Stabilität einstellbar sind. Dies eröffnete die Möglichkeit diese Kohlenstoffpartikel als alternatives und nachhaltiges Rußmaterial einzusetzen.
Weiterhin war es durch die ionothermale Templatierung möglich poröse, dotierte und kontrollierbare Kohlenstoffpartikel mit hohen spezifischen Oberflächen aus den gewählten Präkursorverbindungen zu synthetisieren, die sich für den Einsatz in Superkondensatoren eignen.
Auf diesen Erkenntnissen aufbauend konnten mittels der Rotationsbeschichtung poröse binderfreie und strukturierte Kohlenstofffilme synthetisiert werden, die eine spinodale Struktur aufwiesen. Anhand der Modifikation der Stammlösungskonzentration, der Rotationsgeschwindigkeit und der verwendeten Substrate konnten die Filmdicke (100-1000 nm), die Morphologie und Gesamtoberfläche gezielt beeinflusst werden. Die erweiterte elektrochemische Analyse zeigte außerdem ein sehr gut zugängliches Porensystem der porösen Kohlenstofffilme.
Allumfassend konnten demnach verschiedene Synthesewege für Kohlenstoffmaterialien aus Tanninen aufgezeigt werden, die verschiedenartig strukturiert und kontrolliert werden können und sich für diverse Anwendungsgebiete eignen.
Orthogonal systems for heterologous protein expression as well as for the engineering of synthetic gene regulatory circuits in hosts like Saccharomyces cerevisiae depend on synthetic transcription factors (synTFs) and corresponding cis-regulatory binding sites. We have constructed and characterized a set of synTFs based on either transcription activator-like effectors or CRISPR/Cas9, and corresponding small synthetic promoters (synPs) with minimal sequence identity to the host’s endogenous promoters. The resulting collection of functional synTF/synP pairs confers very low background expression under uninduced conditions, while expression output upon induction of the various synTFs covers a wide range and reaches induction factors of up to 400. The broad spectrum of expression strengths that is achieved will be useful for various experimental setups, e.g., the transcriptional balancing of expression levels within heterologous pathways or the construction of artificial regulatory networks. Furthermore, our analyses reveal simple rules that enable the tuning of synTF expression output, thereby allowing easy modification of a given synTF/synP pair. This will make it easier for researchers to construct tailored transcriptional control systems.
In the present work side-chain polystyrenes were synthesized and characterized, in order to be applied in multilayer OLEDs fabricated by solution process techniques. Manufacture of optoelectronic devices by solution process techniques is meant to decrease significantly fabrication cost and allow large scale production of such devices.
This dissertation focusses in three series, enveloped in two material classes. The two classes differ to each other in the type of charge transport exhibited, either ambipolar transport or electron transport. All materials were applied in all-organic solution processed green Ir-based devices.
In the first part, a series of ambipolar host materials were developed to transport both charge types, holes and electrons, and be applied especially as matrix for green Ir-based emitters. It was possible to increase devices efficacy by modulating the predominant charge transport type. This was achieved by modification of molecules electron transport part with more electron-deficient heterocycles or by extending the delocalization of the LUMO. Efficiencies up to 28.9 cd/A were observed for all-organic solution-process three layer devices.
In the second part, suitability of triarylboranes and tetraphenylsilanes as electron transport materials was studied. High triplet energies were obtained, up to 2.95 eV, by rational combination of both molecular structures. Although the combination of both elements had a low effect in materials electron transport properties, high efficiencies around 24 cd/A were obtained for the series in all-organic solution-processed two layer devices.
In the last part, benzene and pyridine were chosen as the series electron-transport motif. By controlling the relative pyridine content (RPC) solubility into methanol was induced for polystyrenes with bulky side-chains. Materials with RPC ≥ 0.5 could be deposited orthogonally from solution without harming underlying layers. From the best of our knowledge, this is the first time such materials are applied in this architecture showing moderate efficiencies around 10 cd/A in all-organic solution processed OLEDs.
Overall, the outcome of these studies will actively contribute to the current research on materials for all-solution processed OLEDs.
I. Ceric ammonium nitrate (CAN) mediated thiocyanate radical additions to glycals
In this dissertation, a facile entry was developed for the synthesis of 2-thiocarbohydrates and their transformations. Initially, CAN mediated thiocyanation of carbohydrates was carried out to obtain the basic building blocks (2-thiocyanates) for the entire studies. Subsequently, 2-thiocyanates were reduced to the corresponding thiols using appropriate reagents and reaction conditions. The screening of substrates, stereochemical outcome and the reaction mechanism are discussed briefly (Scheme I).
Scheme I. Synthesis of the 2-thiocyanates II and reductions to 2-thiols III & IV.
An interesting mechanism was proposed for the reduction of 2-thiocyanates II to 2-thiols III via formation of a disulfide intermediate. The water soluble free thiols IV were obtained by cleaving the thiocyanate and benzyl groups in a single step. In the subsequent part of studies, the synthetic potential of the 2-thiols was successfully expanded by simple synthetic transformations.
II. Transformations of the 2-thiocarbohydrates
The 2-thiols were utilized for convenient transformations including sulfa-Michael additions, nucleophilic substitutions, oxidation to disulfides and functionalization at the anomeric position. The diverse functionalizations of the carbohydrates at the C-2 position by means of the sulfur linkage are the highlighting feature of these studies. Thus, it creates an opportunity to expand the utility of 2-thiocarbohydrates for biological studies.
Reagents and conditions: a) I2, pyridine, THF, rt, 15 min; b) K2CO3, MeCN, rt, 1 h; c) MeI, K2CO3, DMF, 0 °C, 5 min; d) Ac2O, H2SO4 (1 drop), rt, 10 min; e) CAN, MeCN/H2O, NH4SCN, rt, 1 h; f) NaN3, ZnBr2, iPrOH/H2O, reflux, 15 h; g) NaOH (1 M), TBAI, benzene, rt, 2 h; h) ZnCl2, CHCl3, reflux, 3 h.
Scheme II. Functionalization of 2-thiocarbohydrates.
These transformations have enhanced the synthetic value of 2-thiocarbohydrates for the preparative scale. Worth to mention is the Lewis acid catalyzed replacement of the methoxy group by other nucleophiles and the synthesis of the (2→1) thiodisaccharides, which were obtained with complete β-selectivity. Additionally, for the first time, the carbohydrate linked thiotetrazole was synthesized by a (3 + 2) cycloaddition approach at the C-2 position.
III. Synthesis of thiodisaccharides by thiol-ene coupling.
In the final part of studies, the synthesis of thiodisaccharides by a classical photoinduced thiol-ene coupling was successfully achieved.
Reagents and conditions: 2,2-Dimethoxy-2-phenylacetophenone (DPAP), CH2Cl2/EtOH, hv, rt.
Scheme III. Thiol-ene coupling between 2-thiols and exo-glycals.
During the course of investigations, it was found that the steric hindrance plays an important role in the addition of bulky thiols to endo-glycals. Thus, we successfully screened the suitable substrates for addition of various thiols to sterically less hindered alkenes (Scheme III). The photochemical addition of 2-thiols to three different exo-glycals delivered excellent regio- and diastereoselectivities as well as yields, which underlines the synthetic potential of this convenient methodology.
The title compound was prepared by the reaction of 1,4,10,13-tetraoxa-7,16-diazacyclo-octadecane with 4-chloro-2-methyl-phenoxyacetic acid in a ratio of 1:2. The structure has been proved by the data of elemental analysis, IR spectroscopy, NMR ( 1 H, 13 C) technique and by X-ray diffraction analysis. Intermolecular hydrogen bonds between the azonium protons and oxygen atoms of the carboxylate groups were found. Immunoactive properties of the title compound have been screened. The compound has the ability to suppress spontaneous and Con A-stimulated cell proliferation in vitro and therefore can be considered as immunodepressant.
Graphs are ubiquitous in Computer Science. For this reason, in many areas, it is very important to have the means to express and reason about graph properties. In particular, we want to be able to check automatically if a given graph property is satisfiable. Actually, in most application scenarios it is desirable to be able to explore graphs satisfying the graph property if they exist or even to get a complete and compact overview of the graphs satisfying the graph property.
We show that the tableau-based reasoning method for graph properties as introduced by Lambers and Orejas paves the way for a symbolic model generation algorithm for graph properties. Graph properties are formulated in a dedicated logic making use of graphs and graph morphisms, which is equivalent to firstorder logic on graphs as introduced by Courcelle. Our parallelizable algorithm gradually generates a finite set of so-called symbolic models, where each symbolic model describes a set of finite graphs (i.e., finite models) satisfying the graph property. The set of symbolic models jointly describes all finite models for the graph property (complete) and does not describe any finite graph violating the graph property (sound). Moreover, no symbolic model is already covered by another one (compact). Finally, the algorithm is able to generate from each symbolic model a minimal finite model immediately and allows for an exploration of further finite models. The algorithm is implemented in the new tool AutoGraph.
Swearing in a public place
(2017)
The paper deals with the usage of swear words on the online forum "reddit". Three research questions are dealt with:
How often are swear words used?
How are these swear words received by other users?
Does the topic of the conversation have an influence on the reception and amount of usage of swear words?
The corpus from which the results are taken comprises almost 900 million words. The words are taken from February 2017. Compared to other, similar studies, the corpus is considerably larger and contempory.
In addition, the theoretical part discusses the linguistic basics of swear words. These include concepts such as the theory of politeness, the topic of taboos and its corresponding words and censorship. This is done to explain the factors that influence the use and application of swear words and to explain why swearwords are so special in comparison to other word groups. In addition, further research results from other corpora are presented and compared with the results afterwards. This includes corpora that are also composed of online communication, as well as corpora that reproduce spoken language. The results from all the corpora presented deal with results from the English language.
The results of this study indicate that the swear words on "reddit" are used approximately as often as they are on other platforms. The perception of these swear words is mostly positive, which suggests that the use of swear words on "reddit" is not perceived as impolite. In addition, an influence of the discussion topic on the frequency and reception of swear words could be determined.
Nowadays, the need to protect the environment becomes more urgent than ever. In the field of chemistry, this translates to practices such as waste prevention, use of renewable feedstocks, and catalysis; concepts based on the principles of green chemistry. Polymers are an important product in the chemical industry and are also in the focus of these changes. In this thesis, more sustainable approaches to make two classes of polymers, polypeptoids and polyesters, are described.
Polypeptoids or poly(alkyl-N-glycines) are isomers of polypeptides and are biocompatible, as well as degradable under biologically relevant conditions. In addition to that, they can have interesting properties such as lower critical solution temperature (LCST) behavior. They are usually synthesized by the ring opening polymerization (ROP) of N-carboxy anhydrides (NCAs), which are produced with the use of toxic compounds (e.g. phosgene) and which are highly sensitive to humidity. In order to avoid the direct synthesis and isolation of the NCAs, N-phenoxycarbonyl-protected N-substituted glycines are prepared, which can yield the NCAs in situ. The conditions for the NCA synthesis and its direct polymerization are investigated and optimized for the simplest N-substituted glycine, sarcosine. The use of a tertiary amine in less than stoichiometric amounts compared to the N-phenoxycarbonyl--sarcosine seems to accelerate drastically the NCA formation and does not affect the efficiency of the polymerization. In fact, well defined polysarcosines that comply to the monomer to initiator ratio can be produced by this method. This approach was also applied to other N-substituted glycines.
Dihydroxyacetone is a sustainable diol produced from glycerol, and has already been used for the synthesis of polycarbonates. Here, it was used as a comonomer for the synthesis of polyesters. However, the polymerization of dihydroxyacetone presented difficulties, probably due to the insolubility of the macromolecular chains. To circumvent the problem, the dimethyl acetal protected dihydroxyacetone was polymerized with terephthaloyl chloride to yield a soluble polymer. When the carbonyl was recovered after deprotection, the product was insoluble in all solvents, showing that the carbonyl in the main chain hinders the dissolution of the polymers. The solubility issue can be avoided, when a 1:1 mixture of dihydroxyacetone/ ethylene glycol is used to yield a soluble copolyester.
Anthropogenically amplified erosion leads to increased fine-grained sediment input into the fluvial system in the 15.000 km2 Kharaa River catchment in northern Mongolia and constitutes a major stressing factor for the aquatic ecosystem. This study uniquely combines the application of intensive monitoring, source fingerprinting and catchment modelling techniques to allow for the comparison of the credibility and accuracy of each single method. High-resolution discharge data were used in combination with daily suspended solid measurements to calculate the suspended sediment budget and compare it with estimations of the sediment budget model SedNet. The comparison of both techniques showed that the development of an overall sediment budget with SedNet was possible, yielding results in the same order of magnitude (20.3 kt a- 1 and 16.2 kt a- 1).
Radionuclide sediment tracing, using Be-7, Cs-137 and Pb-210 was applied to differentiate sediment sources for particles < 10μm from hillslope and riverbank erosion and showed that riverbank erosion generates 74.5% of the suspended sediment load, whereas surface erosion contributes 21.7% and gully erosion only 3.8%. The contribution of the single subcatchments of the Kharaa to the suspended sediment load was assessed based on their variation in geochemical composition (e.g. in Ti, Sn, Mo, Mn, As, Sr, B, U, Ca and Sb). These variations were used for sediment source discrimination with geochemical composite fingerprints based on Genetic Algorithm driven Discriminant Function Analysis, the Kruskal–Wallis H-test and Principal Component Analysis. The contributions of the individual sub-catchment varied from 6.4% to 36.2%, generally showing higher contributions from the sub-catchments in the middle, rather than the upstream portions of the study area.
The results indicate that river bank erosion generated by existing grazing practices of livestock is the main cause for elevated fine sediment input. Actions towards the protection of the headwaters and the stabilization of the river banks within the middle reaches were identified as the highest priority. Deforestation and by lodging and forest fires should be prevented to avoid increased hillslope erosion in the mountainous areas. Mining activities are of minor importance for the overall catchment sediment load but can constitute locally important point sources for particular heavy metals in the fluvial system.