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Gegenstand der Dissertation ist die Präsentation von Kleidermode in ihr gewidmeten Sonderausstellungen, die in zunehmender Zahl seit den 1990er Jahren in musealen und musemsähnlichen Kontexten veranstaltet werden. Es geht darum, wie Modekörper und vestimentäre Artefakte in diesen Ausstellungen gezeigt werden und welche ästhetischen Erfahrungen sich für die RezipientInnen aus der jeweiligen Konstellation von vestimentärem Objekt und Inszenierungsmittel ergeben können. Das Augenmerk liegt auf der Spannung zwischen dem visuellen Imperativ musealer Zeigepraktiken und den multisensorischen Qualitäten der Kleidermode, v. a. jener hautsinnlichen, die sich aus dem unmittelbaren Kontakt zwischen Körper und Kleid ergeben.
Die zentrale These ist, dass sich das Hautsinnliche der Kleidermode trotz des Berührungsverbots in vielen Ausstellungsinszenierungen zeigen kann. D. h., dass – entgegen häufig wiederholter Behauptungen – ‚der Körper‘, das Tragen und die Bewegung nicht per se oder komplett aus den Kleidern gewichen sind, werden diese musealisiert und ausgestellt. Es findet eine Verschiebung des Körperlichen und Hautsinnlichen, wie das Anfassen, Tragen und Bewegen, in visuelle Darstellungsformen statt. Hautsinnliche Qualitäten der vestimentären Exponate können, auch in Abhängigkeit von den jeweils verwendeten Präsentationsmitteln, von den BesucherInnen in unterschiedlichen Abstufungen sehend oder buchstäblich gespürt werden.
An konkreten Beispielen wird zum einen das Verhältnis von ausgestelltem Kleid und Präsentationsmittel(n) in den Displays untersucht. Dabei stehen folgende Mittel im Fokus, mit deren Hilfe die vestimentären Exponate zur Schau gestellt werden: Vitrinen, Podeste, Ersatzkörper wie Mannequins, optische Hilfsmittel wie Lupen, Bildmedien oder (bewegte) Installationen. Zum anderen wird analysiert, welche Wirkungen die Arrangements jeweils erzielen oder verhindern können, und zwar in Hinblick auf mögliche ästhetische Erfahrungen, die taktilen, haptischen und kinästhetischen Qualitäten der Exponate als BesucherIn sehend oder buchstäblich zu fühlen oder zu spüren. Ob als Identifikation, Projektion, Haptic Vision – es handelt sich um ästhetische Erfahrungen, die sich aus den modischen Kompetenzen der BetrachterInnen speisen und bei denen sich Visuelles und Hautsinnliches oft überlagern.
In der Untersuchung wird eine vernachlässigte, wenn nicht gar unerwünschte Rezeptionsweise diskutiert, die von den AkteurInnen der spezifischen Debatte bspw. als konsumptives Sehen abgewertet wird. Die von mir vorgeschlagene, stärker differenzierende Perspektive ist zugleich eine Kritik an dem bisherigen Diskurs und seinem eng gefassten, teilweise elitären Verständnis von Museum, Bildung und Wissen, mit dem sich AkteurInnen und Institutionen abgrenzen. Der Spezialdiskurs über musealisierte und exponierte Kleidermode steht zudem exemplarisch für die Diskussion, was das Museum, verstanden als Institution, sein kann und soll(te) und ob (und wenn ja, wie) es sich überhaupt noch von anderen Orten und Räumen klar abgrenzen lässt.
Bobrowski hatte nach dem Abitur die Absicht geäußert, Kunstgeschichte zu studieren, doch Krieg und Kriegsgefangenschaft vereitelten seinen Plan: Der Wehrmachtsangehörige wurde einzig im Winter 1941/1942 für ein Studiensemester an der Universität Berlin vom Kriegsdienst freigestellt. Nachhaltig beeindruckt war Bobrowski insbesondere von der Vorlesung „Deutsche Kunst der Goethezeit“ des Lehrstuhlinhabers Wilhelm Pinder. Trotz eines grundlegenden Einflusses ist indessen zu keinem Zeitpunkt Pinders ideologischer Hintergrund in Bobrowskis Gedichten manifest geworden. Nach der Rückkehr aus sowjetischer Gefangenschaft an Weihnachten 1949 war für den mittlerweile Zweiunddreißigjährigen an ein Studium nicht mehr zu denken. Die lebenslange intermediale Auseinandersetzung mit Werken der bildenden Kunst in seinem Œuvre kann indessen als Ausdruck seiner vielfältigen kulturgeschichtlichen Interessen und Neigungen interpretiert werden. Die Lebensphasen des Dichters korrelieren mit einer motivischen Entwicklung seiner Bildgedichte: Insbesondere half ihm die unantastbare Ästhetik bedeutender Kunstwerke, das Grauen der letzten Kriegsjahre und die Entbehrungen in sowjetischer Kriegsgefangenschaft zu überwinden. Didaktisch-moralische Zielsetzungen prägten zunächst die in den Jahren nach seiner Heimkehr entstandenen Gedichte, bevor sich Bobrowski inhaltlich und formal von diesem Gedichttypus zu lösen vermochte und vermehrt Gedichte zu schreiben begann, die kulturgeschichtliche Dimensionen annahmen und historische, mythologische, biblische und religionsphilosophische Themen in epochenübergreifende Zusammenhänge stellten. Die Gedichte über die Künstler Jawlensky und Calder berühren gleichzeitig kulturlandschaftliche Aspekte. Im letzten Lebensjahrzehnt interessierte sich Bobrowski zunehmend für die Kunst des 20. Jahrhunderts, während die moderne Architektur aus seinem Werk ausgeklammert blieb.
Architektur bildet eine Leitmotivik in Bobrowskis lyrischem Werk. Die übertragene Bedeutungsebene der in den Gedichten benannten sakralen und profanen Einzelbauten, aber auch der städtischen und dörflichen Ensembles sowie einzelner Gebäudeteile, verändert sich mehrfach im Laufe der Jahre. Ausgehend von traditionellen, paargereimten Jugendgedichten in jambischem Versmaß, in denen architektonische Elemente Teil einer Wahrnehmung bilden, die alles Außerästhetische ausblendet, wandelt sich der Sinngehalt der Sakral- und Profanbauten in Bobrowskis lyrischem Werk ein erstes Mal während den Kriegsjahren in Russland, die der Wehrmachtsangehörige am Ilmensee verbracht hat. In den damals entstandenen Oden zeugen die architektonischen Relikte von Leid, Tod und Zerstörung. Noch fehlt indessen der später so zentrale Gedanke der Schuld, der erst im Rückblick auf jene Zeit in den Gedichten, die nach der Rückkehr aus der Kriegsgefangenschaft bis zu Bobrowskis frühem Tod entstanden sind, thematisiert worden ist.
Gegen Ende des Kriegs und in den Jahren der Kriegsgefangenschaft besinnt sich Bobrowski erneut auf Heimatthemen, und die Architektur in seinen Gedichten wird zu einem ästhetisch überhöhten Fluchtpunkt seiner Sehnsucht nach Ostpreußen und dem Memelgebiet. In Kriegsgefangenschaft tritt erstmals der Aspekt des Sublimen in seinen Gedichten auf, und zwar sowohl bezogen auf die Malerei als auch auf die Architektur. Dieser Gedanke wird einerseits nach der Rückkehr nach Berlin in den Gedichten über die Architektur gotischer Kathedralen und das bauliche Erbe des Klassizismus weitergesponnen, doch steht in den damals entstandenen Gedichten das Kulturerbe Europas auch für historisches Unrecht und eine schwere, weit zurückreichende Schuld.
Von dieser auf den ganzen Kontinent bezogenen Kritik wendet sich Bobrowski in den nachfolgenden Jahren ab und konzentriert sich auf die Schuld der Deutschen gegenüber den Völkern Osteuropas. Damit erhält auch die Architektur in seinen Gedichten eine neue Bedeutung. Die Relikte der Ritterburgen des deutschen Ordens zeugen von der Herrschaft der mittelalterlichen Eroberer und verschmelzen dabei mit der Natur: Das Zeichenhafte der Architektur wird Teil der Landschaft. Im letzten Lebensjahrzehnt entstehen vermehrt Gedichte, die sich auf Parkanlagen und städtische Grünräume beziehen.
Der Dichter hat sich nicht nur auf persönliche Erfahrungen, sondern mitunter auch auf Bildquellen abstützt, ohne dass er das Original je gesehen hätte. Nur schwer zugänglich sind die Gedichte über Chagall und Gauguin ohne die Erkenntnis, dass sie sich auf Bildvorlagen in schmalen, populärwissenschaftlichen Büchern beziehen, die Bobrowski jeweils kurz vor der Niederschrift der entsprechenden Gedichte erworben hat. Anders verhält es sich mit jenen russischen Kirchen, die Eingang in sein lyrisches Werk gefunden haben. Bobrowski hat sie alle selbst im Krieg gesehen, und die meisten scheinen noch heute zu bestehen und können mit einiger Sicherheit identifiziert werden, wozu auch die Briefe des Dichters aus jener Zeit beitragen.
The work done during the PhD studies has been focused on measurements of distribution functions of rotating galaxies using integral field spectroscopy observations.
Throughout the main body of research presented here we have been using CALIFA (Calar Alto Legacy Integral Field Area) survey stellar velocity fields to obtain robust measurements of circular velocities for rotating galaxies of all morphological types. A crucial part of the work was enabled by well-defined CALIFA sample selection criteria: it enabled reconstructing sample-independent distributions of galaxy properties.
In Chapter 2, we measure the distribution in absolute magnitude - circular velocity space for a well-defined sample of 199 rotating CALIFA galaxies using their stellar kinematics. Our aim in this analysis is to avoid subjective selection criteria and to take volume and large-scale structure factors into account. Using stellar velocity fields instead of gas emission line kinematics allows including rapidly rotating early type galaxies. Our initial sample contains 277 galaxies with available stellar velocity fields and growth curve r-band photometry. After rejecting 51 velocity fields that could not be modelled due to the low number of bins, foreground contamination or significant interaction we perform Markov Chain Monte Carlo (MCMC) modelling of the velocity fields, obtaining the rotation curve and kinematic parameters and their realistic uncertainties. We perform an extinction correction and calculate the circular velocity v_circ accounting for pressure support a given galaxy has. The resulting galaxy distribution on the M_r - v_circ plane is then modelled as a mixture of two distinct populations, allowing robust and reproducible rejection of outliers, a significant fraction of which are slow rotators. The selection effects are understood well enough that the incompleteness of the sample can be corrected and the 199 galaxies can be weighted by volume and large-scale structure factors enabling us to fit a volume-corrected Tully-Fisher relation (TFR). More importantly, we also provide the volume-corrected distribution of galaxies in the M_r - v_circ plane, which can be compared with cosmological simulations. The joint distribution of the luminosity and circular velocity space densities, representative over the range of -20 > M_r > -22 mag, can place more stringent constraints on the galaxy formation and evolution scenarios than linear TFR fit parameters or the luminosity function alone.
In Chapter 3, we measure one of the marginal distributions of the M_r - v_circ distribution: the circular velocity function of rotating galaxies. The velocity function is a fundamental observable statistic of the galaxy population, being of a similar importance as the luminosity function, but much more difficult to measure. We present the first directly measured circular velocity function that is representative between 60 < v_circ < 320 km s^-1 for galaxies of all morphological types at a given rotation velocity. For the low mass galaxy population 60 < v_circ < 170 km s^-1, we use the HIPASS velocity function. For the massive galaxy population 170 < v_circ < 320 km s^-1, we use stellar circular velocities from CALIFA. The CALIFA velocity function includes homogeneous velocity measurements of both late and early-type rotation-supported galaxies. It has the crucial advantage of not missing gas-poor massive ellipticals that HI surveys are blind to. We show that both velocity functions can be combined in a seamless manner, as their ranges of validity overlap. The resulting observed velocity function is compared to velocity functions derived from cosmological simulations of the z = 0 galaxy population. We find that dark matter-only simulations show a strong mismatch with the observed VF. Hydrodynamic Illustris simulations fare better, but still do not fully reproduce observations.
In Chapter 4, we present some other work done during the PhD studies, namely, a method that improves the precision of specific angular measurements by combining simultaneous Markov Chain Monte Carlo modelling of ionised gas 2D velocity fields and HI linewidths. To test the method we use a sample of 25 galaxies from the Sydney-AAO Multi-object Integral field (SAMI) survey that had matching ALFALFA HI linewidths. Such a method allows constraining the rotation curve both in the inner regions of a galaxy and in its outskirts, leading to increased precision of specific angular momentum measurements. It could be used to further constrain the observed relation between galaxy mass, specific angular momentum and morphology (Obreschkow & Glazebrook 2014).
Mathematical and computational methods are presented in the appendices.
Introduction: Carbohydrate (CHO) and fat are the main substrates to fuel prolonged endurance exercise, each having its oxidation patterns regulated by several factors such as intensity, duration and mode of the activity, dietary intake pattern, muscle glycogen concentrations, gender and training status. Exercising at intensities where fat oxidation rates are high has been shown to induce metabolic benefits in recreational and health-oriented sportsmen. The exercise intensity (Fatpeak) eliciting peak fat oxidation rates is therefore of particular interest when aiming to prescribe exercise for the purpose of fat oxidation and related metabolic effects. Although running and walking are feasible and popular among the target population, no reliable protocols are available to assess Fatpeak as well as its actual velocity (VPFO) during treadmill ergometry. Moreover, to date, it remains unclear how pre-exercise CHO availability modulates the oxidative regulation of substrates when exercise is conducted at the intensity where the individual anaerobic threshold (IAT) is located (VIAT). That is, a metabolic marker representing the upper border where constant load endurance exercise can be sustained, being commonly used to guide athletic training or in performance diagnostics. The research objectives of the current thesis were therefore, 1) to assess the reliability and day-to-day variability of VPFO and Fatpeak during treadmill ergometry running; 2) to assess the impact of high CHO (HC) vs. low CHO (LC) diets (where on the LC day a combination of low CHO diet and a glycogen depleting exercise was implemented) on the oxidative regulation of CHOs and fat while exercise is conducted at VIAT. Methods: Research objective 1: Sixteen recreational athletes (f=7, m=9; 25 ± 3 y; 1.76 ± 0.09 m; 68.3 ± 13.7 kg; 23.1 ± 2.9 kg/m²) performed 2 different running protocols on 3 different days with standardized nutrition the day before testing. At day 1, peak oxygen uptake (VO2peak) and the velocities at the aerobic threshold (VLT) and respiratory exchange ratio (RER) of 1.00 (VRER) were assessed. At days 2 and 3, subjects ran an identical submaximal incremental test (Fat-peak test) composed of a 10 min warm-up (70% VLT) followed by 5 stages of 6 min with equal increments (stage 1 = VLT, stage 5 = VRER). Breath-by-breath gas exchange data was measured continuously and used to determine fat oxidation rates. A third order polynomial function was used to identify VPFO and subsequently Fatpeak. The reproducibility and variability of variables was verified with an intraclass correlation coefficient (ICC), Pearson’s correlation coefficient, coefficient of variation (CV) and the mean differences (bias) ± 95% limits of agreement (LoA). Research objective 2: Sixteen recreational runners (m=8, f=8; 28 ± 3 y; 1.76 ± 0.09 m; 72 ± 13 kg; 23 ± 2 kg/m²) performed 3 different running protocols, each allocated on a different day. At day 1, a maximal stepwise incremental test was implemented to assess the IAT and VIAT. During days 2 and 3, participants ran a constant-pace bout (30 min) at VIAT that was combined with randomly assigned HC (7g/kg/d) or LC (3g/kg/d) diets for the 24 h before testing. Breath-by-breath gas exchange data was measured continuously and used to determine substrate oxidation. Dietary data and differences in substrate oxidation were analyzed with a paired t-test. A two-way ANOVA tested the diet X gender interaction (α = 0.05). Results: Research objective 1: ICC, Pearson’s correlation and CV for VPFO and Fatpeak were 0.98, 0.97, 5.0%; and 0.90, 0.81, 7.0%, respectively. Bias ± 95% LoA was -0.3 ± 0.9 km/h for VPFO and -2 ± 8% of VO2peak for Fatpeak. Research objective 2: Overall, the IAT and VIAT were 2.74 ± 0.39 mmol/l and 11.1 ± 1.4 km/h, respectively. CHO oxidation was 3.45 ± 0.08 and 2.90 ± 0.07 g/min during HC and LC bouts respectively (P < 0.05). Likewise, fat oxidation was 0.13 ± 0.03 and 0.36 ± 0.03 g/min (P < 0.05). Females had 14% (P < 0.05) and 12% (P > 0.05) greater fat oxidation compared to males during HC and LC bouts, respectively. Conclusions: Research objective 1: In summary, relative and absolute reliability indicators for VPFO and Fatpeak were found to be excellent. The observed LoA may now serve as a basis for future training prescriptions, although fat oxidation rates at prolonged exercise bouts at this intensity still need to be investigated. Research objective 2: Twenty-four hours of high CHO consumption results in concurrent higher CHO oxidation rates and overall utilization, whereas maintaining a low systemic CHO availability significantly increases the contribution of fat to the overall energy metabolism. The observed gender differences underline the necessity of individualized dietary planning before exerting at intensities associated with performance exercise. Ultimately, future research should establish how these findings can be extrapolated to training and competitive situations and with that provide trainers and nutritionists with improved data to derive training prescriptions.
The aim of this thesis is to develop approaches to automatically recognise the structure of argumentation in short monological texts. This amounts to identifying the central claim of the text, supporting premises, possible objections, and counter-objections to these objections, and connecting them correspondingly to a structure that adequately describes the argumentation presented in the text.
The first step towards such an automatic analysis of the structure of argumentation is to know how to represent it. We systematically review the literature on theories of discourse, as well as on theories of the structure of argumentation against a set of requirements and desiderata, and identify the theory of J. B. Freeman (1991, 2011) as a suitable candidate to represent argumentation structure. Based on this, a scheme is derived that is able to represent complex argumentative structures and can cope with various segmentation issues typically occurring in authentic text.
In order to empirically test our scheme for reliability of annotation, we conduct several annotation experiments, the most important of which assesses the agreement in reconstructing argumentation structure. The results show that expert annotators produce very reliable annotations, while the results of non-expert annotators highly depend on their training in and commitment to the task.
We then introduce the 'microtext' corpus, a collection of short argumentative texts. We report on the creation, translation, and annotation of it and provide a variety of statistics. It is the first parallel corpus (with a German and English version) annotated with argumentation structure, and -- thanks to the work of our colleagues -- also the first annotated according to multiple theories of (global) discourse structure.
The corpus is then used to develop and evaluate approaches to automatically predict argumentation structures in a series of six studies: The first two of them focus on learning local models for different aspects of argumentation structure. In the third study, we develop the main approach proposed in this thesis for predicting globally optimal argumentation structures: the 'evidence graph' model. This model is then systematically compared to other approaches in the fourth study, and achieves state-of-the-art results on the microtext corpus. The remaining two studies aim to demonstrate the versatility and elegance of the proposed approach by predicting argumentation structures of different granularity from text, and finally by using it to translate rhetorical structure representations into argumentation structures.
Direct anthropogenic influences on the Earth’s subsurface during drilling, extraction or injection activities, can affect land stability by causing subsidence, uplifts or lateral displacements. They can occur in localized as well as in uninhabited and inhabited regions. Thus the associated risks for humans, infrastructure, and environment must be minimized. To achieve this, appropriate surveillance methods must be found that can be used for simultaneous monitoring during such activities. Multi-temporal synthetic aperture radar interferometry (MT-InSAR) methods like the Persistent Scatterer Interferometry (PSI) and the Small BAseline Subsets (SBAS) have been developed as standard approaches for satellite-based surface displacement monitoring. With increasing spatial resolution and availability of SAR sensors in recent years, MT-InSAR can be valuable for the detection and mapping of even the smallest man-made displacements.
This doctoral thesis aims at investigating the capacities of the mentioned standard methods for this purpose, and comprises three main objectives against the backdrop of a user-friendly surveillance service:
(1) the spatial and temporal significance assessment against leveling, (2) the suitability evaluation of PSI and SBAS under different conditions, and (3) the analysis of the link between surface motion and subsurface processes.
Two prominent case studies on anthropogenic induced subsurface processes in Germany serve as the basis for this goal. The first is the distinct urban uplift with severe damages at Staufen im Breisgau that has been associated since 2007 with a failure to implement a shallow geothermal energy supply for an individual building. The second case study considers the pilot project of geological carbon dioxide (CO2) storage at Ketzin, and comprises borehole drilling and fluid injection of more than 67 kt CO2 between 2008 and 2013. Leveling surveys at Staufen and comprehensive background knowledge of the underground processes gained from different kinds of in-situ measurements at both locations deliver a suitable basis for this comparative study and the above stated objectives. The differences in location setting, i.e. urban versus rural site character, were intended to investigate the limitations in the applicability of PSI and SBAS.
For the MT-InSAR analysis, X-band images from the German TerraSAR-X and TanDEM-X satellites were acquired in the standard Stripmap mode with about 3 m spatial resolution in azimuth and range direction. Data acquisition lasted over a period of five years for Staufen (2008-2013), and four years for Ketzin (2009-2013). For the first approximation of the subsurface source, an inversion of the InSAR outcome in Staufen was applied. The modeled uplift based on complex hydromechanical simulations and a correlation analysis with bottomhole pressure data were used for comparison with MT-InSAR measurements at Ketzin.
In response to the defined objectives of this thesis, a higher level of detail can be achieved in mapping surface displacements without in-situ effort by using MT-InSAR in comparison to leveling (1). A clear delineation of the elliptical shaped uplift border and its magnitudes at different parts was possible at Staufen, with the exception of a vegetated area in the northwest. Vegetation coverage and the associated temporal signal decorrelation are the main limitations of MT-InSAR as clearly demonstrated at the Ketzin test site. They result in insufficient measurement point density and unwrapping issues. Therefore, spatial resolutions of one meter or better are recommended to achieve an adequate point density for local displacement analysis and to apply signal noise reduction. Leveling measurements can provide a complementary data source here, but require much effort pertaining to personnel even at the local scale. Horizontal motions could be identified at Staufen by only comparing the temporal evolution of the 1D line of sight (LOS) InSAR measurements with the available leveling data. An exception was the independent LOS decomposition using ascending and descending data sets for the period 2012-2013. The full 3D displacement field representation failed due to insufficient orbit-related, north-south sensitivity of the satellite-based measurements. By using the dense temporal mapping capabilities of the TerraSAR-X/TanDEM-X satellites after every 11 days, the temporal displacement evolution could be captured as good as that with leveling.
With respect to the tested methods and in the view of generality, SBAS should be preferred over PSI (2). SBAS delivered a higher point density, and was therefore less affected by phase unwrapping issues in both case studies. Linking surface motions with subsurface processes is possible when considering simplified geophysical models (3), but it still requires intensive research to gain a deep understanding.
Modern welfare states aim at designing unemployment insurance (UI) schemes which minimize the length of unemployment spells. A variety of institutions and incentives, which are embedded in UI schemes across OECD countries, reflect this attempt. For instance, job seekers entering UI are often provided with personal support through a caseworker. They also face the requirement to regularly submit a minimum number of job applications, which is typically enforced through benefit cuts in the case of non-compliance. Moreover, job seekers may systematically receive information on their re-employment prospects. As a consequence, UI design has become a complex task. Policy makers need to define not only the amount and duration of benefit payments, but also several other choice parameters. These include the intensity and quality of personal support through caseworkers, the level of job search requirements, the strictness of enforcement, and the information provided to unemployed individuals. Causal estimates on how these parameters affect re-employment outcomes are thus central inputs to the design of modern UI systems: how much do individual caseworkers influence the transition out of unemployment? Does the requirement of an additional job application translate into increased job finding? Do individuals behave differently when facing a strict versus mild enforcement system? And how does information on re-employment prospects influence the job search decision? This dissertation proposes four novel research designs to answer this question. Chapters one to three elaborate quasi-experimental identification strategies, which are applied to large-scale administrative data from Switzerland. They, respectively, measure how personal interactions with caseworkers (chapter one), the level of job search requirements (chapter two) and the strictness of enforcement (chapter three) affect re-employment outcomes. Chapter four proposes a structural estimation approach, based on linked survey and administrative data from Germany. It studies how over-optimism on future wage offers affects the decision to search for work, and how the provision of information changes this decision.
Prevalence and Predictors of Sexual Aggression Victimization and Perpetration in Chile and Turkey
(2017)
Background: Although sexual aggression is recognized as a serious issue worldwide, the current knowledge base is primarily built on evidence from Western countries, particularly the U.S. For the present doctoral research, Chile and Turkey were selected based on theoretical considerations to examine the prevalence as well as predictors of sexual aggression victimization and perpetration. The first aim of this research project was to systematically review the available evidence provided by past studies on this topic within each country. The second aim was to empirically study the prevalence of experiencing and engaging in sexual aggression since the age of consent among college students in Chile and Turkey. The third aim was to conduct cross-cultural analyses examining pathways to victimization and perpetration based on a two-wave longitudinal design.
Methods: This research adopted a gender-inclusive approach by considering men and women in both victim and perpetrator roles. For the systematic reviews, multiple-stage literature searches were performed, and based on a predefined set of eligibility criteria, 28 studies in Chile and 56 studies in Turkey were identified for inclusion. A two-wave longitudinal study was conducted to examine the prevalence and predictors of sexual aggression among male and female college students in Chile and Turkey. Self-reports of victimization and perpetration were assessed with a Chilean Spanish or Turkish version of the Sexual Aggression and Victimization Scale. Two path models were conceptualized in which participants’ risky sexual scripts for consensual sex, risky sexual behavior, sexual self-esteem, sexual assertiveness, and religiosity were assessed at T1 and used as predictors of sexual aggression victimization and perpetration at T2 in the following 12 months, mediated through past victimization or perpetration, respectively. The models differed in that sexual assertiveness was expected to serve different functions for victimization (refusal assertiveness negatively linked to victimization) and perpetration (initiation assertiveness positively linked to perpetration).
Results: Both systematic reviews revealed that victimization was addressed by all included studies, but data on perpetration was severely limited. A great heterogeneity not only in victimization rates but also in predictors was found, which may be attributed to a lack of conceptual and methodological consistency across studies. The empirical analysis of the prevalence of sexual aggression in Chile revealed a victimization rate of 51.9% for women and 48.0% for men, and a perpetration rate of 26.8% for men and 16.5% for women. In the Turkish original data, victimization was reported by 77.6% of women and 65.5% of men, whereas, again, lower rates were found for perpetration, with 28.9% of men and 14.2% of women reporting at least one incident. The cross-cultural analyses showed, as expected, that risky sexual scripts informed risky sexual behavior, and thereby indirectly increased the likelihood of victimization and perpetration at T2 in both samples. More risky sexual scripts were also linked to lower levels of refusal assertiveness in both samples, indirectly increasing the vulnerability to victimization at T2. High sexual self-esteem decreased the probability of victimization at T2 through higher refusal assertiveness as well as through less risky sexual behavior also in both samples, whereas it increased the odds of perpetration at T2 via higher initiation assertiveness in the Turkish sample only. Furthermore, high religiosity decreased the odds of perpetration and victimization at T2 through less risky sexual scripts and less risky sexual behavior in both samples. It reduced the vulnerability to victimization through less risky sexual scripts and higher refusal assertiveness in the Chilean sample only. In the Turkish sample only, it increased the odds of perpetration and victimization through lower sexual self-esteem.
Conclusions: The findings showed that sexual aggression is a widespread problem in both Chile and Turkey, contributing cross-cultural evidence to the international knowledge base and indicating the clear need for implementing policy measures and prevention strategies in each country. Based on the results of the prospective analyses, concrete implications for intervention efforts are discussed.
This is a cumulative dissertation comprising three original studies (one published, one in revision, one submitted; Effective December 2017) investigating how reptile species in arid Australia respond to various climatic parameters at different spatial scales and analysing the two potential main underlying mechanisms: thermoregulatory behaviour and species interactions. This dissertation combines extensive individual-based field data across trophic levels, selected field experiments, statistical analyses, and predictive modelling techniques. Mechanisms and processes detected in this dissertation can now be used to predict potential future changes in the community of arid-zone lizards. This knowledge will help improving our fundamental understanding of the consequences of global change and thereby prevent biodiversity loss in a vulnerable ecosystem.
Adipositas wird mit einer Vielzahl schwerwiegender Folgeerkrankungen in Verbindung gebracht. Eine Gewichtsreduktion führt zu einer Verbesserung der metabolischen Folgen der Adipositas. Es ist bekannt, dass die Mehrzahl der adipösen Personen in den Monaten nach der Gewichtsreduktion einen Großteil des abgenommenen Gewichts wieder zunimmt. Nichtsdestotrotz existiert eine hohe Variabilität hinsichtlich des Langzeiterfolges einer Gewichtsreduktion. Der erfolgreiche Erhalt des reduzierten Körpergewichts einiger Personen führt zu der Frage nach den Faktoren, die einen Gewichtserhalt beeinflussen, mit dem Ziel einen Ansatzpunkt für mögliche Therapiestrategien zu identifizieren.
In der vorliegenden Arbeit wurde im Rahmen einer kontrollierten, randomisierten Studie mit 143 übergewichtigen Probanden untersucht, ob nach einer dreimonatigen Gewichtsreduktion eine zwölfmonatige gewichtsstabilisierende Lebensstilintervention einen Einfluss auf die Veränderungen der neuroendokrinen Regelkreisläufe und damit auf den langfristigen Gewichtserhalt über einen Zeitraum von achtzehn Monaten hat.
Hierbei wurde im Vergleich der beiden Behandlungsgruppen primär festgestellt, dass die multimodale Lebensstilintervention zu einer Gewichtstabilisierung über die Dauer dieser zwölfmonatigen Behandlungsphase führte. In der Kontrollgruppe kam es zu einer moderaten Gewichtszunahme . Dadurch war nach Beendigung der Interventionsphase der BMI der Teilnehmer in der Kontrollgruppe höher als der in der Interventionsgruppe (34,1±6,0 kg*m-2 vs. 32,4±5,7 kg*m-2; p<0,01).
Während der Nachbeobachtungszeit war die Interventionsgruppe durch eine signifikant stärkere Gewichtswiederzunahme im Vergleich zur Kontrollgruppe gekennzeichnet, so dass der BMI zwischen beiden Behandlungsgruppen bereits sechs Monate nach der Intervention keinen Unterschied mehr aufwies.
Bezüglich der hormonellen Veränderung durch die Gewichtsreduktion wurde, wie erwartet, eine Auslenkung des endokrinen Systems beobachtet. Jedoch konnte kein Unterschied der untersuchten Hormone im Vergleich der beiden Behandlungsgruppen ausfindig gemacht werden.
Im Verlauf der Gewichtsabnahme und der anschließenden Studienphasen zeigten sich tendenziell drei verschiedene Verlaufsmuster in den hormonellen Veränderungen. Nach einer zusätzlichen Adjustierung auf den jeweiligen BMI des Untersuchungszeitpunktes konnte für die TSH-Spiegel (p<0,05), die Schilddrüsenhormone (p<0,001) und für die IGF 1-Spiegel (p<0,001) eine über die Studienzeit anhaltende Veränderung festgestellt werden.
Abschließend wurde behandlungsgruppenunabhängig untersucht, ob die Hormonspiegel nach Gewichtsreduktion oder ob die relative hormonelle Veränderung während der Gewichtsreduktion prädiktiv für den Erfolg der Gewichterhaltungsphase ist. Hier fand sich für die Mehrzahl der hormonellen Parameter kein Effekt auf die Langzeitentwicklung der Gewichtszunahme. Jedoch konnte gezeigt werden, dass eine geringere Abnahme der 24h Urin-Metanephrin-Ausscheidung während der Gewichtsabnahmephase mit einem besseren Erfolg bezüglich des Gewichtserhalts über die achtzehnmonatige Studienzeit assoziiert war (standardisiertes Beta= -0,365; r2=0,133 p<0,01). Die anderen hormonellen Achsen zeigten keinen nachweislichen Effekt.
Im kognitiven Vulnerabilitäts-Stress-Modell der Depression von A.T. Beck (1967, 1976) spielen dysfunktionale Einstellungen bei der Entstehung von Depression in Folge von erlebtem Stress eine zentrale Rolle. Diese Theorie prägt seit Jahrzehnten die ätiologische Erforschung der Depression, jedoch ist die Bedeutung dysfunktionaler Einstellungen im Prozess der Entstehung einer Depression insbesondere im Kindes- und Jugendalter nach wie vor unklar. Die vorliegende Arbeit widmet sich einigen in der bisherigen Forschung wenig behandelten Fragen. Diese betreffen u. a. die Möglichkeit nichtlinearer Effekte dysfunktionaler Einstellungen, Auswirkungen einer Stichprobenselektion, Entwicklungseffekte sowie die Spezifität etwaiger Zusammenhänge für eine depressive Symptomatik.
Zur Beantwortung dieser Fragen wurden Daten von zwei Messzeitpunkten der PIER-Studie, eines großangelegten Längsschnittprojekts über Entwicklungsrisiken im Kindes- und Jugendalter, genutzt. Kinder und Jugendliche im Alter von 9 bis 18 Jahren berichteten zweimal im Abstand von ca. 20 Monaten im Selbstberichtsverfahren über ihre dysfunktionalen Einstellungen, Symptome aus verschiedenen Störungsbereichen sowie über eingetretene Lebensereignisse.
Die Ergebnisse liefern Evidenz für ein Schwellenmodell, in dem dysfunktionale Einstellungen unabhängig von Alter und Geschlecht nur im höheren Ausprägungsbereich eine Wirkung als Vulnerabilitätsfaktor zeigen, während im niedrigen Ausprägungsbereich keine Zusammenhänge zur späteren Depressivität bestehen. Eine Wirkung als Vulnerabilitätsfaktor war zudem nur in der Subgruppe der anfänglich weitgehend symptomfreien Kinder und Jugendlichen zu beobachten. Das Schwellenmodell erwies sich als spezifisch für eine depressive Symptomatik, es zeigten sich jedoch auch (teilweise ebenfalls nichtlineare) Effekte dysfunktionaler Einstellungen auf die Entwicklung von Essstörungssymptomen und aggressivem Verhalten. Bei 9- bis 13-jährigen Jungen standen dysfunktionale Einstellungen zudem in Zusammenhang mit einer Tendenz, Stress in Leistungskontexten herbeizuführen.
Zusammen mit den von Sahyazici-Knaak (2015) berichteten Ergebnissen aus der PIER-Studie weisen die Befunde darauf hin, dass dysfunktionale Einstellungen im Kindes- und Jugendalter – je nach betrachteter Subgruppe – Ursache, Symptom und Konsequenz der Depression darstellen können. Die in der vorliegenden Arbeit gezeigten nichtlinearen Effekte dysfunktionaler Einstellungen und die Effekte der Stichprobenselektion bieten eine zumindest teilweise Erklärung für die Heterogenität früherer Forschungsergebnisse. Insgesamt lassen sie auf komplexe – und nicht ausschließlich negative – Auswirkungen dysfunktionaler Einstellungen schließen. Für eine adäquate Beurteilung der „Dysfunktionalität“ der von A.T. Beck so betitelten Einstellungen erscheint daher eine Berücksichtigung der betrachteten Personengruppe, der absoluten Ausprägungen und der fraglichen Symptomgruppen geboten.
Trends in precipitation over Germany and the Rhine basin related to changes in weather patterns
(2017)
Precipitation as the central meteorological feature for agriculture, water security, and human well-being amongst others, has gained special attention ever since. Lack of precipitation may have devastating effects such as crop failure and water scarcity. Abundance of precipitation, on the other hand, may as well result in hazardous events such as flooding and again crop failure. Thus, great effort has been spent on tracking changes in precipitation and relating them to underlying processes. Particularly in the face of global warming and given the link between temperature and atmospheric water holding capacity, research is needed to understand the effect of climate change on precipitation.
The present work aims at understanding past changes in precipitation and other meteorological variables. Trends were detected for various time periods and related to associated changes in large-scale atmospheric circulation. The results derived in this thesis may be used as the foundation for attributing changes in floods to climate change. Assumptions needed for the downscaling of large-scale circulation model output to local climate stations are tested and verified here.
In a first step, changes in precipitation over Germany were detected, focussing not only on precipitation totals, but also on properties of the statistical distribution, transition probabilities as a measure for wet/dry spells, and extreme precipitation events.
Shifting the spatial focus to the Rhine catchment as one of the major water lifelines of Europe and the largest river basin in Germany, detected trends in precipitation and other meteorological variables were analysed in relation to states of an ``optimal'' weather pattern classification. The weather pattern classification was developed seeking the best skill in explaining the variance of local climate variables.
The last question addressed whether observed changes in local climate variables are attributable to changes in the frequency of weather patterns or rather to changes within the patterns itself. A common assumption for a downscaling approach using weather patterns and a stochastic weather generator is that climate change is expressed only as a changed occurrence of patterns with the pattern properties remaining constant. This assumption was validated and the ability of the latest generation of general circulation models to reproduce the weather patterns was evaluated.
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Precipitation changes in Germany in the period 1951-2006 can be summarised briefly as negative in summer and positive in all other seasons. Different precipitation characteristics confirm the trends in total precipitation: while winter mean and extreme precipitation have increased, wet spells tend to be longer as well (expressed as increased probability for a wet day followed by another wet day). For summer the opposite was observed: reduced total precipitation, supported by decreasing mean and extreme precipitation and reflected in an increasing length of dry spells.
Apart from this general summary for the whole of Germany, the spatial distribution within the country is much more differentiated. Increases in winter precipitation are most pronounced in the north-west and south-east of Germany, while precipitation increases are highest in the west for spring and in the south for autumn. Decreasing summer precipitation was observed in most regions of Germany, with particular focus on the south and west.
The seasonal picture, however, was again differently represented in the contributing months, e.g.\ increasing autumn precipitation in the south of Germany is formed by strong trends in the south-west in October and in the south-east in November. These results emphasise the high spatial and temporal organisation of precipitation changes.
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The next step towards attributing precipitation trends to changes in large-scale atmospheric patterns was the derivation of a weather pattern classification that sufficiently stratifies the local climate variables under investigation. Focussing on temperature, radiation, and humidity in addition to precipitation, a classification based on mean sea level pressure, near-surface temperature, and specific humidity was found to have the best skill in explaining the variance of the local variables. A rather high number of 40 patterns was selected, allowing typical pressure patterns being assigned to specific seasons by the associated temperature patterns. While the skill in explaining precipitation variance is rather low, better skill was achieved for radiation and, of course, temperature.
Most of the recent GCMs from the CMIP5 ensemble were found to reproduce these weather patterns sufficiently well in terms of frequency, seasonality, and persistence.
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Finally, the weather patterns were analysed for trends in pattern frequency, seasonality, persistence, and trends in pattern-specific precipitation and temperature. To overcome uncertainties in trend detection resulting from the selected time period, all possible periods in 1901-2010 with a minimum length of 31 years were considered. Thus, the assumption of a constant link between patterns and local weather was tested rigorously. This assumption was found to hold true only partly. While changes in temperature are mainly attributable to changes in pattern frequency, for precipitation a substantial amount of change was detected within individual patterns.
Magnitude and even sign of trends depend highly on the selected time period. The frequency of certain patterns is related to the long-term variability of large-scale circulation modes.
Changes in precipitation were found to be heterogeneous not only in space, but also in time - statements on trends are only valid for the specific time period under investigation. While some part of the trends can be attributed to changes in the large-scale circulation, distinct changes were found within single weather patterns as well.
The results emphasise the need to analyse multiple periods for thorough trend detection wherever possible and add some note of caution to the application of downscaling approaches based on weather patterns, as they might misinterpret the effect of climate change due to neglecting within-type trends.
Steep mountain channels are an important component of the fluvial system. On geological timescales, they shape mountain belts and counteract tectonic uplift by erosion. Their channels are strongly coupled to hillslopes and they are often the main source of sediment transported downstream to low-gradient rivers and to alluvial fans, where commonly settlements in mountainous areas are located. Hence, mountain streams are the cause for one of the main natural hazards in these regions. Due to climate change and a pronounced populating of mountainous regions the attention given to this threat is even growing. Although quantitative studies on sediment transport have significantly advanced our knowledge on measuring and calibration techniques we still lack studies of the processes within mountain catchments. Studies examining the mechanisms of energy and mass exchange on small temporal and spatial scales in steep streams remain sparse in comparison to low-gradient alluvial channels.
In the beginning of this doctoral project, a vast amount of experience and knowledge of a steep stream in the Swiss Prealps had to be consolidated in order to shape the principal aim of this research effort. It became obvious, that observations from within the catchment are underrepresented in comparison to experiments performed at the catchment’s outlet measuring fluxes and the effects of the transported material. To counteract this imbalance, an examination of mass fluxes within the catchment on the process scale was intended. Hence, this thesis is heavily based on direct field observations, which are generally rare in these environments in quantity and quality. The first objective was to investigate the coupling of the channel with surrounding hillslopes, the major sources of sediment. This research, which involved the monitoring of the channel and adjacent hillslopes, revealed that alluvial channel steps play a key role in coupling of channel and hillslopes. The observations showed that hillslope stability is strongly associated with the step presence and an understanding of step morphology and stability is therefore crucial in understanding sediment mobilization. This finding refined the way we think about the sediment dynamics in steep channels and motivated continued research of the step dynamics. However, soon it became obvious that the technological basis for developing field tests and analyzing the high resolution geometry measured in the field was not available. Moreover, for many geometrical quantities in mountain channels definitions and a clear scientific standard was not available. For example, these streams are characterized by a high spatial variability of the channel banks, preventing straightforward calculations of the channel width without a defined reference. Thus, the second and inevitable part of this thesis became the development and evaluation of scientific tools in order to investigate the geometrical content of the study reach thoroughly. The developed framework allowed the derivation of various metrics of step and channel geometry which facilitated research on the a large data set of observations of channel steps. In the third part, innovative, physically-based metrics have been developed and compared to current knowledge on step formation, suggested in the literature. With this analyses it could be demonstrated that the formation of channel steps follow a wide range of hydraulic controls. Due to the wide range of tested parameters channel steps observed in a natural stream were attributed to different mechanisms of step formation, including those based on jamming and those based on key-stones. This study extended our knowledge on step formation in a steep stream and harmonized different, often time seen as competing, processes of step formation. This study was based on observations collected at one point in time. In the fourth part of this project, the findings of the snap-shot observations were extended in the temporal dimension and the derived concepts have been utilized to investigate reach-scale step patterns in response to large, exceptional flood events. The preliminary results of this work based on the long-term analyses of 7 years of long profile surveys showed that the previously observed channel-hillslope mechanism is the responsible for the short-term response of step formation.
The findings of the long-term analyses of step patterns drew a bow to the initial observations of a channel-hillslope system which allowed to join the dots in the dynamics of steep stream. Thus, in this thesis a broad approach has been chosen to gain insights into the complex system of steep mountain rivers. The effort includes in situ field observations (article I), the development of quantitative scientific tools (article II), the reach-scale analyses of step-pool morphology (article III) and its temporal evolution (article IV). With this work our view on the processes within the catchment has been advanced towards a better mechanistic understanding of these fluvial system relevant to improve applied scientific work.
With recent advances in the area of information extraction, automatically extracting structured information from a vast amount of unstructured textual data becomes an important task, which is infeasible for humans to capture all information manually. Named entities (e.g., persons, organizations, and locations), which are crucial components in texts, are usually the subjects of structured information from textual documents. Therefore, the task of named entity mining receives much attention. It consists of three major subtasks, which are named entity recognition, named entity linking, and relation extraction.
These three tasks build up an entire pipeline of a named entity mining system, where each of them has its challenges and can be employed for further applications. As a fundamental task in the natural language processing domain, studies on named entity recognition have a long history, and many existing approaches produce reliable results. The task is aiming to extract mentions of named entities in text and identify their types. Named entity linking recently received much attention with the development of knowledge bases that contain rich information about entities. The goal is to disambiguate mentions of named entities and to link them to the corresponding entries in a knowledge base. Relation extraction, as the final step of named entity mining, is a highly challenging task, which is to extract semantic relations between named entities, e.g., the ownership relation between two companies.
In this thesis, we review the state-of-the-art of named entity mining domain in detail, including valuable features, techniques, evaluation methodologies, and so on. Furthermore, we present two of our approaches that focus on the named entity linking and relation extraction tasks separately.
To solve the named entity linking task, we propose the entity linking technique, BEL, which operates on a textual range of relevant terms and aggregates decisions from an ensemble of simple classifiers. Each of the classifiers operates on a randomly sampled subset of the above range. In extensive experiments on hand-labeled and benchmark datasets, our approach outperformed state-of-the-art entity linking techniques, both in terms of quality and efficiency.
For the task of relation extraction, we focus on extracting a specific group of difficult relation types, business relations between companies. These relations can be used to gain valuable insight into the interactions between companies and perform complex analytics, such as predicting risk or valuating companies. Our semi-supervised strategy can extract business relations between companies based on only a few user-provided seed company pairs. By doing so, we also provide a solution for the problem of determining the direction of asymmetric relations, such as the ownership_of relation. We improve the reliability of the extraction process by using a holistic pattern identification method, which classifies the generated extraction patterns. Our experiments show that we can accurately and reliably extract new entity pairs occurring in the target relation by using as few as five labeled seed pairs.
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.
Background and objectives: Age-related losses of lower extremity muscle strength/power and deficits in static and particularly dynamic balance are associated with impaired functional performance and the occurrence of falls. It has been shown that balance and resistance training have the potential to improve balance and muscle strength in healthy older adults. However, it is still open to debate how the effectiveness of balance and resistance training in older adults is influenced by different factors. This includes the role of trunk muscle strength, the comprehensive effects of combined balance and resistance training, and the role of exercise supervision. Therefore, the primary objectives of this doctoral thesis are to investigate the relationship between trunk muscle strength and balance performance and to examine the effects of an expert-based balance and resistance training protocol on various measures of balance and lower extremity muscle strength/power in older adults. Furthermore, the impact of supervised versus unsupervised balance and/or resistance training interventions in the elderly will be evaluated.
Methods: Healthy older adults aged 63-80 years were included in a cross-sectional study, a longitudinal study, and a meta-analysis (range group means meta-analysis: 65.3-81.1 years) registering balance and muscle strength/power performance. Different measures of balance (i.e., static/dynamic, proactive, reactive) were examined using clinical (e.g., Romberg test) and instrumented tests (e.g., 10 meter walking test on a sensor-equipped walkway). Isometric strength of the trunk muscles was assessed using instrumented trunk muscle strength apparatus and lower extremity dynamic muscle strength/power was examined using clinical tests (e.g., Chair Stand Test). Further, a combined balance and resistance training protocol was applied to examine training-induced effects on balance and muscle strength/power as well as the role of supervision in older adults.
Results: Findings revealed that measures of trunk muscle strength and static steady-state balance as well as specific measures of dynamic steady-state balance were significantly associated in the elderly (0.42 ≤ r ≤ 0.57). Combined balance and resistance training significantly improved older adults' static/dynamic steady-state (e.g., Romberg test; habitual gait speed), pro-active (e.g., Timed Up and Go Test), and reactive balance (e.g., Push and Release Test) as well as muscle strength/power (e.g., Chair Stand Test) (0.62 ≤ Cohen’s d ≤ 2.86; all p < 0.05). Supervised compared to unsupervised balance and/or resistance training was superior in enhancing older adults' balance and muscle strength/power performance regarding all observed outcome categories [longitudinal study: effects for the supervised group 0.26 ≤ d ≤ 2.86, effects for the unsupervised group 0.06 ≤ d ≤ 2.30; meta-analysis: all between-subject standardized mean differences (SMDbs) in favor of the supervised training programs 0.24-0.53]. The meta-analysis additionally showed larger effects in favor of supervised interventions when compared to completely unsupervised interventions (0.28 ≤ SMDbs ≤ 1.24). These effects in favor of the supervised programs faded when compared with studies that implemented a small amount of supervised sessions in their unsupervised interventions (−0.06 ≤ SMDbs ≤ 0.41).
Conclusions: Trunk muscle strength is associated with steady-state balance performance and may therefore be integrated in fall-preventive exercise interventions for older adults. The examined positive effects on a large number of important intrinsic fall risk factors (e.g., balance deficits, muscle weakness) imply that particularly the combination of balance and resistance training appears to be a feasible and effective exercise intervention for fall prevention. Owing to the beneficial effects of supervised compared to unsupervised interventions, supervised sessions should be integrated in fall-preventive balance and/or resistance training programs for older adults.
Ecosystem services (ESs) are defined as the contributions that ecosystems make to human wellbeing and are increasingly being used as an approach to explore the importance of ecosystems for humans through their valuation. Although value plurality has been recognised long before the mainstreaming of ESs research, socio-cultural valuation is still underrepresented in ESs assessments. It is the central goal of this PhD dissertation to explore the ability of socio-cultural valuation methods for the operationalisation of ESs research in land management. To address this, I formulated three research objectives that are briefly outlined below and relate to the three studies conducted during this dissertation.
The first objective relates to the assessment of the current role of socio-cultural valuation in ESs research. Human values are central to ESs research yet non-monetary socio-cultural valuation methods have been found underrepresented in the field of ESs science. In regard to the unbalanced consideration of value domains and conceptual uncertainties, I perform a systematic literature review aiming to answer the research question: To what extent have socio-cultural values been addressed in ESs assessments.
The second objective aims to test socio-cultural valuation methods of ESs and their relevance for land use preferences by exploring their methodological opportunities and limitations. Socio-cultural valuation methods have only recently become a focus in ESs research and therefore bear various uncertainties in regard to their methodological implications. To overcome these uncertainties, I analysed responses to a visitor survey. The research questions related to the second objective were: What are the implications of different valuation methods for ESs values? To what extent are land use preferences explained by socio-cultural values of ESs?
The third objective addressed in this dissertation is the implementation of ESs research into land management through socio-cultural valuation. Though it is emphasised that the ESs approach can assist decision making, there is little empirical evidence of the effect of ESs knowledge on land management. I proposed a way to implement transdisciplinary, spatially explicit research on ESs by answering the following research questions: Which landscape features underpinning ESs supply are considered in land management? How can participatory approaches accounting for ESs be operationalised in land management?
The empirical research resulted in five main findings that provide answers to the research questions. First, this dissertation provides evidence that socio-cultural values are an integral part of ESs research. I found that they can be assessed for provisioning, regulating, and cultural services though they are linked to cultural services to a greater degree. Socio-cultural values have been assessed by monetary and non-monetary methods and their assessment is effectively facilitated by stakeholder participation. Second, I found that different methods of socio-cultural valuation revealed different information. Whereas rating revealed a general value of ESs, weighting was found more suitable to identify priorities across ESs. Value intentions likewise differed in the distribution of values, generally implying a higher value for others than for respondents themselves. Third, I showed that ESs values were distributed similarly across groups with differing land use preferences. Thus, I provided empirical evidence that ESs values and landscape values should not be used interchangeably. Fourth, I showed which landscape features important for ESs supply in a Scottish regional park are not sufficiently accounted for in the current management strategy. This knowledge is useful for the identification of priority sites for land management. Finally, I provide an approach to explore how ESs knowledge elicited by participatory mapping can be operationalised in land management. I demonstrate how stakeholder knowledge and values can be used for the identification of ESs hotspots and how these hotspots can be compared to current management priorities.
This dissertation helps to bridge current gaps of ESs science by advancing the understanding of the current role of socio-cultural values in ESs research, testing different methods and their relevance for land use preferences, and implementing ESs knowledge into land management. If and to what extent ESs and their values are implemented into ecosystem management is mainly the choice of the management. An advanced understanding of socio-cultural valuation methods contributes to the normative basis of this management, while the proposal for the implementation of ESs in land management presents a practical approach of how to transfer this type of knowledge into practice. The proposed methods for socio-cultural valuation can support guiding land management towards a balanced consideration of ESs and conservation goals.
Das Ziel der Arbeit ist die Entwicklung eines heuristischen Bezugsrahmens zur Erklärung der Komplexität im Kontext von Industrie 4.0 und der demografischen Entwicklung aus strukturationstheoretischer Sicht. Dabei sind in Bezug auf die zukünftig zu erwartenden kognitiven Anforderungen an die Beschäftigten die Fragen essentiell, vor welchen Herausforderungen Unternehmen bezüglich der Einstellung und dem Verhalten sowie dem Erfahrungswissen der Beschäftigten stehen und welche Lösungsansätze sich im Umgang mit den Herausforderungen in der Praxis bisher als hilfreich erweisen.
In Kapitel 1 erfolgt zunächst die Beschreibung der Ausgangslage. Es werden die Begriffe Industrie 4.0 und demografische Entwicklung inhaltlich diskutiert und in einen theoretischen Zusammenhang gebracht.
In Kapitel 2 erfolgt die theoretische Fundierung der Arbeit. Dabei wird eine strukturationstheoretische Sicht auf Unternehmen als soziotechnische Systeme eingenommen. Durch diese „nicht deterministische“ Sichtweise wird ein prozessualer Blick auf den Wandlungsprozess in Unternehmen geschaffen, der es möglich macht, die Beschäftigten als aktiv handelnde Akteure im Sinne von „organisieren“ zur Erklärung möglicher Zusammenhänge zwischen Industrie 4.0 und der demografischen Entwicklung mit einzubeziehen. Der soziotechnische Systemansatz und die Strukturationstheorie bilden in diesem Sinne den „Kern“ des zu entwickelnden heuristischen Bezugsrahmens.
Die inhaltliche Gestaltung des theoriebasierten heuristischen Bezugsrahmens erfolgt in Kapitel 3 und Kapitel 4.
Kapitel 3 beschreibt ausgewählte Aspekte zukünftiger Anforderungen an die Arbeit, die durch eine systematische Aufbereitung des derzeitigen Forschungsstandes zu Industrie 4.0 ermittelt wurden. Sie bilden die „Gestaltungsgrenzen“, innerhalb derer sich je nach betrieblicher Situation unterschiedliche neue oder geänderte Anforderungen an die Beschäftigten bei der Gestaltung von Industrie 4.0 ableiten lassen.
In Kapitel 4 werden ausgewählte Aspekte menschlichen Handelns am Beispiel älterer Beschäftigter in Form zweier Schwerpunkte beschrieben.
Der erste Schwerpunkt betrifft mögliche Einflussfaktoren auf die Einstellung und das Verhalten älterer Beschäftigter im Wandlungsprozess aufgrund eines vorherrschenden Altersbildes im Unternehmen. Grundlage hierzu bildete die Stigmatisierungstheorie als interaktionistischer Ansatz der Sozialtheorie.
Mit dem zweiten Schwerpunkt, den ausgewählten handlungstheoretischen Aspekten der Alternsforschung aus der Entwicklungspsychologie, wird eine Lebensspannenperspektive eingenommen. Inhaltlich werden die komplexitätsinduzierten Faktoren, die sich aus handlungstheoretischer Perspektive mit der Adaptation von älteren Beschäftigten an veränderte äußere und persönliche Lebensbedingungen beschäftigen, systematisiert.
Anschließend wird auf Grundlage der bisherigen theoretischen Vorüberlegungen ein erster theoriebasierter Bezugsrahmen abgeleitet.
Kapitel 5 und Kapitel 6 beschreiben den empirischen Teil, die Durchführung teilstrukturierter Interviews, der Arbeit. Ziel der empirischen Untersuchung war es, neben der theoretischen Fundierung den theoriebasierten heuristischen Bezugsrahmen um Praxiserfahrungen zu konkretisieren und gegebenenfalls zu ergänzen. Hierzu wurde auf Grundlage des theoriebasierten heuristischen Bezugsrahmens mittels teilstrukturierter Interviews das Erfahrungswissen von 23 Experten in persönlichen Gesprächen abgefragt.
Nachdem in Kapitel 5 die Vorgehensweise der empirischen Untersuchung beschrieben wird, erfolgt in Kapitel 6 die Beschreibung der Ergebnisse aus der qualitativen Befragung. Hierzu werden aus den persönlichen Gesprächen zentrale Einflussfaktoren bei der Gestaltung und Umsetzung von Industrie 4.0 im Kontext mit der demografischen Entwicklung analysiert und in die übergeordneten Kategorien Handlungskompetenzen, Einstellung/ Verhalten sowie Erfahrungswissen geclustert.
Anschließend wird der theoriebasierte heuristische Bezugsrahmen durch die übergeordneten Kategorien und Faktoren aus den Expertengesprächen konkretisiert und ergänzt.
In Kapitel 7 werden auf Grundlage des heuristischen Bezugsrahmens sowie der Empfehlungen aus den Experteninterviews beispielhaft Implikationen für die Praxis abgeleitet. Es werden Interventionsmöglichkeiten zur Unterstützung einer positiven Veränderungsbereitschaft und einem positiven Veränderungsverhalten für den Strukturwandel aufgezeigt. Hierzu gehören die Anpassung des Führungsverhaltens im Wandlungsprozess, der Umgang mit der Paradoxie von Stabilität und Flexibilität, der Umgang mit Altersstereotypen in Unternehmen, die Unterstützung von Strategien zu Selektion, Optimierung und Kompensation sowie Maßnahmen zur Ausrichtung von Aktivitäten an die Potenzialrisiken der Beschäftigten.
Eine Zusammenfassung, ein Resümee und ein Ausblick erfolgen abschließend in Kapitel 8.
This dissertation explores whether the processing of ellipsis is affected by changes in the complexity of the antecedent, either due to added linguistic material or to the presence of a temporary ambiguity. Murphy (1985) hypothesized that ellipsis is resolved via a string copying procedure when the antecedent is within the same sentence, and that copying longer strings takes more time. Such an account also implies that the antecedent is copied without its structure, which in turn implies that recomputing its syntax and semantics may be necessary at the ellipsis gap. Alternatively, several accounts predict null effects of antecedent complexity, as well as no reparsing. These either involve a structure copying mechanism that is cost-free and whose finishing time is thus independent of the form of the antecedent (Frazier & Clifton, 2001), treat ellipsis as a pointer into content-addressable memory with direct access (Martin & McElree, 2008, 2009), or assume that one structure is ‘shared’ between antecedent and gap (Frazier & Clifton, 2005).
In a self-paced reading study on German sluicing, temporarily ambiguous garden-path clauses were used as antecedents, but no evidence of reparsing in the form of a slowdown at the ellipsis site was found. Instead, results suggest that antecedents which had been reanalyzed from an initially incorrect structure were easier to retrieve at the gap. This finding that can be explained within the framework of cue-based retrieval parsing (Lewis & Vasishth, 2005), where additional syntactic operations on a structure yield memory reactivation effects.
Two further self-paced reading studies on German bare argument ellipsis and English verb phrase ellipsis investigated if adding linguistic content to the antecedent would increase processing times for the ellipsis, and whether insufficiently demanding comprehension tasks may have been responsible for earlier null results (Frazier & Clifton, 2000; Martin & McElree, 2008). It has also been suggested that increased antecedent complexity should shorten rather than lengthen retrieval times by providing more unique memory features (Hofmeister, 2011). Both experiments failed to yield reliable evidence that antecedent complexity affects ellipsis processing times in either direction, irrespectively of task demands.
Finally, two eye-tracking studies probed more deeply into the proposed reactivation-induced speedup found in the first experiment. The first study used three different kinds of French garden-path sentences as antecedents, with two of them failing to yield evidence for reactivation. Moreover, the third sentence type showed evidence suggesting that having failed to assign a structure to the antecedent leads to a slowdown at the ellipsis site, as well as regressions towards the ambiguous part of the sentence. The second eye-tracking study used the same materials as the initial self-paced reading study on German, with results showing a pattern similar to the one originally observed, with some notable differences.
Overall, the experimental results are compatible with the view that adding linguistic material to the antecedent has no or very little effect on the ease with which ellipsis is resolved, which is consistent with the predictions of cost-free copying, pointer-based approaches and structure sharing. Additionally, effects of the antecedent’s parsing history on ellipsis processing may be due to reactivation, the availability of multiple representations in memory, or complete failure to retrieve a matching target.
According to the classical plume hypothesis, mantle plumes are localized upwellings of hot, buoyant material in the Earth’s mantle. They have a typical mushroom shape, consisting of a large plume head, which is associated with the formation of voluminous flood basalts (a Large
Igneous Province) and a narrow plume tail, which generates a linear, age-progressive chain of volcanic edifices (a hotspot track) as the tectonic plate migrates over the relatively stationary plume. Both plume heads and tails reshape large areas of the Earth’s surface over many tens of millions of years.
However, not every plume has left an exemplary record that supports the classical hypothesis. The main objective of this thesis is therefore to study how specific hotspots have created the crustal thickness pattern attributed to their volcanic activities. Using regional geodynamic
models, the main chapters of this thesis address the challenge of deciphering the three individual (and increasingly complex) Réunion, Iceland, and Kerguelen hotspot histories, especially focussing on the interactions between the respective plume and nearby spreading ridges.
For this purpose, the mantle convection code ASPECT is used to set up three-dimensional numerical models, which consider the specific local surroundings of each plume by prescribing time-dependent boundary conditions for temperature and mantle flow. Combining reconstructed plate boundaries and plate motions, large-scale global flow velocities and an inhomogeneous lithosphere thickness distribution together with a dehydration rheology represents a novel setup for regional convection models.
The model results show the crustal thickness pattern produced by the plume, which is compared to present-day topographic structures, crustal thickness estimates and age determinations of volcanic provinces associated with hotspot activity. Altogether, the model results agree well
with surface observations. Moreover, the dynamic development of the plumes in the models provide explanations for the generation of smaller, yet characteristic volcanic features that were previously unexplained. Considering the present-day state of a model as a prediction for the
current temperature distribution in the mantle, it cannot only be compared to observations on the surface, but also to structures in the Earth’s interior as imaged by seismic tomography.
More precisely, in the case of the Réunion hotspot, the model demonstrates how the distinctive gap between the Maldives and Chagos is generated due to the combination of the ridge geometry and plume-ridge interaction. Further, the Rodrigues Ridge is formed as the surface expression
of a long-distance sublithospheric flow channel between the upwelling plume and the closest ridge segment, confirming the long-standing hypothesis of Morgan (1978) for the first time in a dynamic context. The Réunion plume has been studied in connection with the seismological
RHUM-RUM project, which has recently provided new seismic tomography images that yield an excellent match with the geodynamic model.
Regarding the Iceland plume, the numerical model shows how plume material may have accumulated in an east-west trending corridor of thin lithosphere across Greenland and resulted in simultaneous melt generation west and east of Greenland. This provides an explanation for the
extremely widespread volcanic material attributed to magma production of the Iceland hotspot and demonstrates that the model setup is also able to explain more complicated hotspot histories. The Iceland model results also agree well with newly derived seismic tomographic images.
The Kerguelen hotspot has an extremely complex history and previous studies concluded that the plume might be dismembered or influenced by solitary waves in its conduit to produce the reconstructed variable melt production rate. The geodynamic model, however, shows that a constant plume influx can result in a variable magma production rate if the plume interacts with nearby mid-ocean ridges. Moreover, the Ninetyeast Ridge in the model is created by on-ridge activities, while the Kerguelen plume was located beneath the Australian plate. This is also a contrast to earlier studies, which described the Ninetyeast Ridge as the result of the Indian plate passing over the plume. Furthermore, the Amsterdam-Saint Paul Plateau in the model is the result of plume material flowing from the upwelling toward the Southeast Indian Ridge, whereas previous geochemical studies attributed that volcanic province to a separate deep plume.
In summary, the three case studies presented in this thesis consistently highlight the importance of plume-ridge interaction in order to reconstruct the overall volcanic hotspot record as well as specific smaller features attributed to a certain hotspot. They also demonstrate that it is not necessary to attribute highly complicated properties to a specific plume in order to account for complex observations. Thus, this thesis contributes to the general understanding of plume dynamics and extends the very specific knowledge about the Réunion, Iceland, and Kerguelen mantle plumes.
Die vorliegende Arbeit mit dem Titel „Eine Frage der Zeit. Wie Einflüsse individueller Merkmale auf Einkommen bei Frauen über ihre familiären Verpflichtungen vermittelt werden“ geht der Frage der Heterogenität bei weiblichen Einkommensergebnissen nach. Dabei steht die Thematik der individuellen Investitionen in die familiäre Arbeit als erklärender Faktor im Vordergrund und es wird der Frage nachgegangen, warum die einen Frauen viele und andere weniger häusliche Verpflichtungen übernehmen. Hierfür werden das individuelle Humankapital der Frauen, ihre Werteorientierungen und individuelle berufliche Motivationen aus der Jugendzeit und im Erwachsenenalter herangezogen. Die analysierten Daten (Daten der LifE-Studie) repräsentieren eine Langzeitperspektive vom 16. bis zum 45. Lebensjahr der befragten Frauen. Zusammenfassend kann im Ergebnis gezeigt werden, dass ein Effekt familiärer Verpflichtungen auf Einkommensergebnisse bei Frauen im frühen und mittleren Erwachsenenalter als Zeiteffekt über die investierte Erwerbsarbeitszeit vermittelt wird. Die Relevanz privater Routinearbeiten für Berufserfolge von Frauen und insbesondere Müttern stellt somit eine Frage der Zeit dar. Weiterhin kann für individuelle Einflüsse auf Einkommen bei Frauen gezeigt werden, dass höhere zeitliche Investitionen in den Beruf von Frauen mit hohem Bildungsniveau als indirect-only-Mediation nur über die Umverteilung häuslicher Arbeiten erklärbar werden. Frauen sind demnach zwar Gewinnerinnen der Bildungsexpansion. Die Bildungsexpansion stellt jedoch auch die Geschichte der Entstehung eines Vereinbarkeitskonflikts für eben diese Frauen dar, weil die bis heute virulenten Beharrungskräfte hinsichtlich der Frauen zugeschriebenen familiären Verpflichtungen mit ihren gestiegenen beruflichen Erwartungen und Chancen kollidieren. Die Arbeit leistet in ihren Analyseresultaten einen wichtigen Beitrag zur Erklärung heterogener Investitionen von Frauen in den Beruf und ihrer Einkommensergebnisse aus dem Privaten heraus.
In this work the human AOX1 was characterized and detailed aspects regarding the expression, the enzyme kinetics and the production of reactive oxygen species (ROS) were investigated. The hAOX1 is a cytosolic enzyme belonging to the molybdenum hydroxylase family. Its catalytically active form is a homodimer with a molecular weight of 300 kDa. Each monomer (150 kDa) consists of three domains: a N-terminal domain (20 kDa) containing two [2Fe-2S] clusters, a 40 kDa intermediate domain containing a flavin adenine dinucleotide (FAD), and a C-terminal domain (85 kDa) containing the substrate binding pocket and the molybdenum cofactor (Moco). The hAOX1 has an emerging role in the metabolism and pharmacokinetics of many drugs, especially aldehydes and N- heterocyclic compounds.
In this study, the hAOX1 was hetereogously expressed in E. coli TP1000 cells, using a new codon optimized gene sequence which improved the expressed protein yield of around 10-fold compared to the previous expression systems for this enzyme. To increase the catalytic activity of hAOX1, an in vitro chemical sulfuration was performed to favor the insertion of the equatorial sulfido ligand at the Moco with consequent increased enzymatic activity of around 10-fold. Steady-state kinetics and inhibition studies were performed using several substrates, electron acceptors and inhibitors. The recombinant hAOX1 showed higher catalytic activity when molecular oxygen was used as electron acceptor. The highest turn over values were obtained with phenanthridine as substrate. Inhibition studies using thioridazine (phenothiazine family), in combination with structural studies performed in the group of Prof. M.J. Romão, Nova Universidade de Lisboa, showed a new inhibition site located in proximity of the dimerization site of hAOX1. The inhibition mode of thioridazine resulted in a noncompetitive inhibition type. Further inhibition studies with loxapine, a thioridazine-related molecule, showed the same type of inhibition. Additional inhibition studies using DCPIP and raloxifene were carried out.
Extensive studies on the FAD active site of the hAOX1 were performed. Twenty new hAOX1 variants were produced and characterized. The hAOX1 variants generated in this work were divided in three groups: I) hAOX1 single nucleotide polymorphisms (SNP) variants; II) XOR- FAD loop hAOX1 variants; III) additional single point hAOX1 variants. The hAOX1 SNP variants G46E, G50D, G346R, R433P, A439E, K1231N showed clear alterations in their catalytic activity, indicating a crucial role of these residues into the FAD active site and in relation to the overall reactivity of hAOX1.
Furthermore, residues of the bovine XOR FAD flexible loop (Q423ASRREDDIAK433) were introduced in the hAOX1. FAD loop hAOX1 variants were produced and characterized for their stability and catalytic activity. Especially the variants hAOX1 N436D/A437D/L438I, N436D/A437D/L438I/I440K and Q434R/N436D/A437D/L438I/I440K showed decreased catalytic activity and stability. hAOX1 wild type and variants were tested for reactivity toward NADH but no reaction was observed.
Additionally, the hAOX1 wild type and variants were tested for the generation of reactive oxygen species (ROS). Interestingly, one of the SNP variants, hAOX1 L438V, showed a high ratio of superoxide prodction. This result showed a critical role for the residue Leu438 in the mechanism of oxygen radicals formation by hAOX1. Subsequently, further hAOX1 variants having the mutated Leu438 residue were produced. The variants hAOX1 L438A, L438F and L438K showed superoxide overproduction of around 85%, 65% and 35% of the total reducing equivalent obtained from the substrate oxidation.
The results of this work show for the first time a characterization of the FAD active site of the hAOX1, revealing the importance of specific residues involved in the generation of ROS and effecting the overall enzymatic activity of hAOX1. The hAOX1 SNP variants presented here indicate that those allelic variations in humans might cause alterations ROS balancing and clearance of drugs in humans.
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.
Self-adaptive data quality
(2017)
Carrying out business processes successfully is closely linked to the quality of the data inventory in an organization. Lacks in data quality lead to problems: Incorrect address data prevents (timely) shipments to customers. Erroneous orders lead to returns and thus to unnecessary effort. Wrong pricing forces companies to miss out on revenues or to impair customer satisfaction. If orders or customer records cannot be retrieved, complaint management takes longer. Due to erroneous inventories, too few or too much supplies might be reordered.
A special problem with data quality and the reason for many of the issues mentioned above are duplicates in databases. Duplicates are different representations of same real-world objects in a dataset. However, these representations differ from each other and are for that reason hard to match by a computer. Moreover, the number of required comparisons to find those duplicates grows with the square of the dataset size. To cleanse the data, these duplicates must be detected and removed. Duplicate detection is a very laborious process. To achieve satisfactory results, appropriate software must be created and configured (similarity measures, partitioning keys, thresholds, etc.). Both requires much manual effort and experience.
This thesis addresses automation of parameter selection for duplicate detection and presents several novel approaches that eliminate the need for human experience in parts of the duplicate detection process.
A pre-processing step is introduced that analyzes the datasets in question and classifies their attributes semantically. Not only do these annotations help understanding the respective datasets, but they also facilitate subsequent steps, for example, by selecting appropriate similarity measures or normalizing the data upfront. This approach works without schema information.
Following that, we show a partitioning technique that strongly reduces the number of pair comparisons for the duplicate detection process. The approach automatically finds particularly suitable partitioning keys that simultaneously allow for effective and efficient duplicate retrieval. By means of a user study, we demonstrate that this technique finds partitioning keys that outperform expert suggestions and additionally does not need manual configuration. Furthermore, this approach can be applied independently of the attribute types.
To measure the success of a duplicate detection process and to execute the described partitioning approach, a gold standard is required that provides information about the actual duplicates in a training dataset. This thesis presents a technique that uses existing duplicate detection results and crowdsourcing to create a near gold standard that can be used for the purposes above. Another part of the thesis describes and evaluates strategies how to reduce these crowdsourcing costs and to achieve a consensus with less effort.
Die Arktis erwärmt sich schneller als der Rest der Erde. Die Auswirkungen manifestieren sich unter Anderem in einer verstärkten Erwärmung der arktischen Grenzschicht. Diese Arbeit befasst sich mit Wechselwirkungen zwischen synoptischen Zyklonen und der arktischen Atmosphäre auf lokalen bis überregionalen Skalen. Ausgangspunkt dafür sind Messdaten und Modellsimulationen für den Zeitraum der N-ICE2015 Expedition, die von Anfang Januar bis Ende Juni 2015 im arktischen Nordatlantiksektor stattgefunden hat.
Anhand von Radiosondenmessungen lassen sich Auswirkungen von synoptischen Zyklonen am deutlichsten im Winter erkennen, da sie durch die Advektion warmer und feuchter Luftmassen in die Arktis den Zustand der Atmosphäre von einem strahlungs-klaren in einen strahlungs-opaken ändern. Obwohl dieser scharfe Kontrast nur im Winter existiert, zeigt die Analyse, dass der integrierte Wasserdampf als Indikator für die Advektion von Luftmassen aus niedrigen Breiten in die Arktis auch im Frühjahr geeignet ist. Neben der Advektion von Luftmassen wird der Einfluss der Zyklonen auf die statische Stabilität charakterisiert. Beim Vergleich der N-ICE2015 Beobachtungen mit der SHEBA Kampagne (1997/1998), die über dickerem Eis stattfand, finden sich trotz der unterschiedlichen Meereisregime Ähnlichkeiten in der statischen Stabilität der Atmosphäre. Die beobachteten Differenzen in der Stabilität lassen sich auf Unterschiede in der synoptischen Aktivität zurückführen. Dies lässt vermuten, dass die dünnere Eisdecke auf saisonalen Zeitskalen nur einen geringen Einfluss auf die thermodynamische Struktur der arktischen Troposphäre besitzt, solange eine dicke Schneeschicht sie bedeckt. Ein weiterer Vergleich mit den parallel zur N-ICE2015 Kampagne gestarteten Radiosonden der AWIPEV Station in Ny-Åesund, Spitzbergen, macht deutlich, dass die synoptischen Zyklonen oberhalb der Orographie auf saisonalen Zeitskalen das Wettergeschehen bestimmen.
Des Weiteren werden für Februar 2015 die Auswirkungen von in der Vertikalen variiertem Nudging auf die Entwicklung der Zyklonen am Beispiel des hydrostatischen regionalen Klimamodells HIRHAM5 untersucht. Es zeigt sich, dass die Unterschiede zwischen den acht Modellsimulationen mit abnehmender Anzahl der genudgten Level zunehmen. Die größten Differenzen resultieren vornehmlich aus dem zeitlichen Versatz der Entwicklung synoptischer Zyklonen. Zur Korrektur des Zeitversatzes der Zykloneninitiierung genügt es bereits, Nudging in den unterstem 250 m der Troposphäre anzuwenden. Daneben findet sich zwischen den genudgten HIRHAM5-Simulation und den in situ Messungen der gleiche positive Temperaturbias, den auch ERA-Interim besitzt. Das freie HIRHAM hingegen reproduziert das positive Ende der N-ICE2015 Temperaturverteilung gut, besitzt aber einen starken negativen Bias, der sehr wahrscheinlich aus einer Unterschätzung des Feuchtegehalts resultiert. An Beispiel einer Zyklone wird gezeigt, dass Nudging Einfluss auf die Lage der Höhentiefs besitzt, die ihrerseits die Zyklonenentwicklung am Boden beeinflussen. Im Weiteren wird mittels eines für kleine Ensemblegrößen geeigneten Varianzmaßes eine statistische Einschätzung der Wirkung des Nudgings auf die Vertikale getroffen. Es wird festgestellt, dass die Ähnlichkeit der Modellsimulationen in der unteren Troposphäre generell höher ist als darüber und in 500 hPa ein lokales Minimum besitzt.
Im letzten Teil der Analyse wird die Wechselwirkung der oberen und unteren Stratosphäre anhand zuvor betrachteter Zyklonen mit Daten der ERA-Interim Reanalyse untersucht. Lage und Ausrichtung des Polarwirbels erzeugten ab Anfang Februar 2015 eine ungewöhnlich große Meridionalkomponente des Tropopausenjets, die Zugbahnen in die zentrale Arktis begünstigte. Am Beispiel einer Zyklone wird die Übereinstimmung der synoptischen Entwicklung mit den theoretischen Annahmen über den abwärts gerichteten Einfluss der Stratosphäre auf die Troposphäre hervorgehoben. Dabei spielt die nicht-lineare Wechselwirkung zwischen der Orographie Grönlands, einer Intrusion stratosphärischer Luft in die Troposphäre sowie einer in Richtung Arktis propagierender Rossby-Welle eine tragende Rolle. Als Indikator dieser Wechselwirkung werden horizontale Signaturen aus abwechselnd aufsteigender und absinkender Luft innerhalb der Troposphäre identifiziert.
The valorization of carbohydrates is one of the most promising fields in green chemistry, as it enables to produce bulk chemicals and fuels out of renewable and abundant resources, instead of further exploiting fossil feedstocks. The focus in this thesis is the conversion of fructose, using dehydration and hydrodeoxygenation reactions. The main goal is to find an easy continuous process, including the solubility of the sugar in a green solvent, the conversion over a solid acid as well as over a metal@tungsten carbide catalyst.
At the beginning of this thesis, solid acid catalysts are synthesized by using carbohydrate material like glucose and starch at high temperatures (up to 600 °C). Additionally a third carbon is synthesized, using an activation method based on Ca(OH)2. After carbonization and further sulfonation, using fuming sulfuric acid, the three resulting catalysts are characterized together with sulfonated carbon black and Amberlyst 15 as references. In order to test all solid acid catalysts in reaction, a 250 mm x 4.6 mm stainless steel column is used as a fixed-bed continuous reactor. The temperature (110 °C to 250 °C) and residence time (2 to 30 minutes) is varied, and a direct relationship between contact time and selectivity is determined. The reaction mechanism, as well as the product distribution is showing a dehydration step of fructose towards 5-hydroxymethylfurfural (HMF). These furan-ring molecules are considered as “sleeping giants”, due to the possibility of using them as fuel, but also for upgrading them to chemicals like terephthalic acid or p-xylene. Consecutive reactions are producing levulinic acid, as well as condensation products with ethanol and formic acid. The activated carbon is additionally showing a 2 % yield of 2,5-Dimethylfuran (DMF) production, pointing towards the extraordinary properties of this catalyst. Without a metal catalyst present, what is normally necessary for hydrogenation reactions, a transferhydrogenation (with formic acid) is observed. The active catalyst was therefore carbon itself, what activated the hydrogen on its surface. This phenomenon was just very rarely observed so far. Expensive noble metals are the material of choice, when it comes to hydrogenation reactions nowadays and cheaper alternatives are necessary.
By postulating a similar electronic structure of tungsten carbide (WC) to platinum by Lewy and Boudart, research is focusing on the replacement of Pt. The production of nano-sized tungsten carbide particles (7.5 ± 2.5 nm, 70 m2 g-1) is enabled by the so called “urea glass route” and its catalytic performances are compared to commercial material. It is shown, that the activity is strongly dependent on the size of the particles as well as the surface area. Nano-sized tungsten carbide is showing activity for hydrogenation reactions under mild conditions (maximum 150 °C, 30 bar). This material therefore opens up new possibilities for replacing the rare and expensive platinum with tungsten carbide based catalysts.
Additionally different metal nanoparticles of palladium, copper and nickel are deposited on top of WC to further promote its reactivity. The nickel nanoparticles are strongly connected to WC and showed the best activity as well as selectivity for upgrading HMF with hydrodeoxygenation. The Ni@WC is not leaching and is showing very good hydrodeoxygenation properties with DMF yields up to 90 percent. Copper@WC is not showing good activity and palladium@WC enables undesired consecutive reactions, hydrogenating the furan ring system.
In order to enable the upgrade of fructose to DMF directly in a continuous system, the current H CUBE Pro TM hydrogenation system is customized with a second reaction column. A 250 mm x 4.6 mm stainless steel reactor column is connected ahead of the hydrogen insertion, enabling the dehydration of fructose to HMF derivatives, before pumping these products into the second column for hydrogenation. The overall residence time in the two column reactor system is 14 minutes. The overall results are an almost full conversion with a yield of 38.5 % DMF and 47 % yield of EL. The main disadvantage is the formation of higher mass products, so called humins, which start depositing on top of the catalysts, blocking their active sites.
In general it can be stated, that a two column system goes along with a higher investment as well as more maintenance costs, compared to a one column catalytic approach. To develop a catalyst, which is on the one hand able to dehydrate as well as hydrodeoxygenate the reactants, is aimed for at the last part of the thesis. The activated carbon however shows already activity for hydrodeoxygenation without any metal present and offers itself therefore as an alternative to overcome the temperature instability of Amberlyst 15 (max. 120 °C) for a combined DMF production directly from fructose. The activity for the upgrade to DMF is increased from 2 % to 12 % DMF yield in one mixed continuous column.
In order to scale up the entire one column approach, an 800 mm x 28.5 mm inner diameter column was planned and manufactured. The system is scaled up and assembled, whereas this flow reactor system is able to be run with 50 mL min-1 maximum flow rate, to stand a pressure of maximum 100 bar and be heated to around 500 °C. The tubing and connections, as well as the used devices are planned according to be safe and easy in use. The scaled-up approach offers a reaction column 120 times bigger (510 ml) then the first extension of the commercial system. This further extension offers the possibility of ranging between 1 and 1000 mL min-1, making it possible to use the approach in pilot plant applications.
Development of a reliable and environmentally friendly synthesis for fluorescence carbon nanodots
(2017)
Carbon nanodots (CNDs) have generated considerable attention due to their promising properties, e.g. high water solubility, chemical inertness, resistance to photobleaching, high biocompatibility and ease of functionalization. These properties render them ideal for a wide range of functions, e.g. electrochemical applications, waste water treatment, (photo)catalysis, bio-imaging and bio-technology, as well as chemical sensing, and optoelectronic devices like LEDs. In particular, the ability to prepare CNDs from a wide range of accessible organic materials makes them a potential alternative for conventional organic dyes and semiconductor quantum dots (QDs) in various applications. However, current synthesis methods are typically expensive and depend on complex and time-consuming processes or severe synthesis conditions and toxic chemicals. One way to reduce overall preparation costs is the use of biological waste as starting material. Hence, natural carbon sources such as pomelo peal, egg white and egg yolk, orange juice, and even eggshells, to name a few; have been used for the preparation of CNDs. While the use of waste is desirable, especially to avoid competition with essential food production, most starting-materials lack the essential purity and structural homogeneity to obtain homogeneous carbon dots. Furthermore, most synthesis approaches reported to date require extensive purification steps and have resulted in carbon dots with heterogeneous photoluminescent properties and indefinite composition. For this reason, among others, the relationship between CND structure (e.g. size, edge shape, functional groups and overall composition) and photophysical properties is yet not fully understood. This is particularly true for carbon dots displaying selective luminescence (one of their most intriguing properties), i.e. their PL emission wavelength can be tuned by varying the excitation wavelength.
In this work, a new reliable, economic, and environmentally-friendly one-step synthesis is established to obtain CNDs with well-defined and reproducible photoluminescence (PL) properties via the microwave-assisted hydrothermal treatment of starch, carboxylic acids and Tris-EDTA (TE) buffer as carbon- and nitrogen source, respectively. The presented microwave-assisted hydrothermal precursor carbonization (MW-hPC) is characterized by its cost-efficiency, simplicity, short reaction times, low environmental footprint, and high yields of approx. 80% (w/w). Furthermore, only a single synthesis step is necessary to obtain homogeneous water-soluble CNDs with no need for further purification.
Depending on starting materials and reaction conditions different types of CNDs have been prepared. The as-prepared CNDs exhibit reproducible, highly homogeneous and favourable PL properties with narrow emission bands (approx. 70nm FWHM), are non-blinking, and are ready to use without need for further purification, modification or surface passivation agents. Furthermore, the CNDs are comparatively small (approx. 2.0nm to 2.4nm) with narrow size distributions; are stable over a long period of time (at least one year), either in solution or as a dried solid; and maintain their PL properties when re-dispersed in solution. Depending on CND type, the PL quantum yield (PLQY) can be adjusted from as low as 1% to as high as 90%; one of the highest reported PLQY values (for CNDs) so far.
An essential part of this work was the utilization of a microwave synthesis reactor, allowing various batch sizes and precise control over reaction temperature and -time, pressure, and heating- and cooling rate, while also being safe to operate at elevated reaction conditions (e.g. 230 ±C and 30 bar). The hereby-achieved high sample throughput allowed, for the first time, the thorough investigation of a wide range of synthesis parameters, providing valuable insight into the CND formation. The influence of carbon- and nitrogen source, precursor concentration and -combination, reaction time and -temperature, batch size, and post-synthesis purification steps were carefully investigated regarding their influence on the optical properties of as-synthesized CNDs. In addition, the change in photophysical properties resulting from the conversion of CND solution into solid and back into the solution was investigated. Remarkably, upon freeze-drying the initial brown CND-solution turns into a non-fluorescent white/slightly yellow to brown solid which recovers PL in aqueous solution. Selected CND samples were also subject to EDX, FTIR, NMR, PL lifetime (TCSPC), particle size (TEM), TGA and XRD analysis. Besides structural characterization, the pH- and excitation dependent PL characteristics (i.e. selective luminescence) were examined; giving inside into the origin of photophysical properties and excitation dependent behaviour of CNDs. The obtained results support the notion that for CNDs the nature of the surface states determines the PL properties and that excitation dependent behaviour is caused by the “Giant Red-Edge Excitation Shift” (GREES).
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.
In the arable soil landscape of hummocky ground moraines, an erosion-affected spatial differentiation of soils can be observed. Man-made erosion leads to soil profile modifications along slopes with changed solum thickness and modified properties of soil horizons due to water erosion in combination with tillage operations. Soil erosion creates, thereby, spatial patterns of soil properties (e.g., texture and organic matter content) and differences in crop development. However, little is known about the manner in which water fluxes are affected by soil-crop interactions depending on contrasting properties of differently-developed soil horizons and how water fluxes influence the carbon transport in an eroded landscape. To identify such feedbacks between erosion-induced soil profile modifications and the 1D-water and solute balance, high-precision weighing lysimeters equipped with a wide range of sensor technique were filled with undisturbed soil monoliths that differed in the degree of past soil erosion. Furthermore, lysimeter effluent concentrations were analyzed for dissolved carbon fractions in bi-weekly intervals.
The water balance components measured by high precision lysimeters varied from the most eroded to the less eroded monolith up to 83 % (deep drainage) primarily caused due to varying amounts of precipitation and evapotranspiration for a 3-years period. Here, interactions between crop development and contrasting rainfall interception by above ground biomass could explain differences in water balance components. Concentrations of dissolved carbon in soil water samples were relatively constant in time, suggesting carbon leaching was mainly affected by water fluxes in this observation period. For the lysimeter-based water balance analysis, a filtering scheme was developed considering temporal autocorrelation. The minute-based autocorrelation analysis of mass changes from lysimeter time series revealed characteristic autocorrelation lengths ranging from 23 to 76 minutes. Thereby, temporal autocorrelation provided an optimal approximation of precipitation quantities. However, the high temporal resolution in lysimeter time series is restricted by the lengths of autocorrelation.
Erosion-induced but also gradual changes in soil properties were reflected by dynamics of soil water retention properties in the lysimeter soils. Short-term and long-term hysteretic water retention data suggested seasonal wettability problems of soils increasingly limited rewetting of previously dried pore regions. Differences in water retention were assigned to soil tillage operations and the erosion history at different slope positions. The threedimensional spatial pattern of soil types that result from erosional soil profile modifications were also reflected in differences of crop root development at different landscape positions. Contrasting root densities revealed positive relations of root and aboveground plant characteristics. Differences in the spatially-distributed root growth between different eroded soil types provided indications that root development was affected by the erosion-induced soil evolution processes.
Overall, the current thesis corroborated the hypothesis that erosion-induced soil profile modifications affect the soil water balance, carbon leaching and soil hydraulic properties, but also the crop root system is influenced by erosion-induced spatial patterns of soil properties in the arable hummocky post glacial soil landscape. The results will help to improve model predictions of water and solute movement in arable soils and to understand interactions between soil erosion and carbon pathways regarding sink-or-source terms in landscapes.
The first main goal of this thesis is to develop a concept of approximate differentiability of higher order for subsets of the Euclidean space that allows to characterize higher order rectifiable sets, extending somehow well known facts for functions. We emphasize that for every subset A of the Euclidean space and for every integer k ≥ 2 we introduce the approximate differential of order k of A and we prove it is a Borel map whose domain is a (possibly empty) Borel set. This concept could be helpful to deal with higher order rectifiable sets in applications.
The other goal is to extend to general closed sets a well known theorem of Alberti on the second order rectifiability properties of the boundary of convex bodies. The Alberti theorem provides a stratification of second order rectifiable subsets of the boundary of a convex body based on the dimension of the (convex) normal cone. Considering a suitable generalization of this normal cone for general closed subsets of the Euclidean space and employing some results from the first part we can prove that the same stratification exists for every closed set.
Nanolenses are linear chains of differently-sized metal nanoparticles, which can theoretically provide extremely high field enhancements. The complex structure renders their synthesis challenging and has hampered closer analyses so far. Here, the technique of DNA origami was used to self-assemble DNA-coated 10 nm, 20 nm, and 60 nm gold or silver nanoparticles into gold or silver nanolenses. Three different geometrical arrangements of gold nanolenses were assembled, and for each of the three, sets of single gold nanolenses were investigated in detail by atomic force microscopy, scanning electron microscopy, dark-field scattering and Raman spectroscopy. The surface-enhanced Raman scattering (SERS) capabilities of the single nanolenses were assessed by labelling the 10 nm gold nanoparticle selectively with dye molecules. The experimental data was complemented by finite-difference time-domain simulations. For those gold nanolenses which showed the strongest field enhancement, SERS signals from the two different internal gaps were compared by selectively placing probe dyes on the 20 nm or 60 nm gold particles. The highest enhancement was found for the gap between the 20 nm and 10 nm nanoparticle, which is indicative of a cascaded field enhancement. The protein streptavidin was labelled with alkyne groups and served as a biological model analyte, bound between the 20 nm and 10 nm particle of silver nanolenses. Thereby, a SERS signal from a single streptavidin could be detected. Background peaks observed in SERS measurements on single silver nanolenses could be attributed to amorphous carbon. It was shown that the amorphous carbon is generated in situ.
Background: Obesity is thought to be the consequence of an unhealthy nutrition and a lack of physical activity. Although the resulting metabolic alterations such as impaired glucose homeostasis and insulin sensitivity can usually be improved by physical activity, some obese patients fail to enhance skeletal muscle metabolic health with exercise training. Since this might be largely heritable, maternal nutrition during pregnancy and lactation is hypothesized to impair offspring skeletal muscle physiology.
Objectives: This PhD thesis aims to investigate the consequences of maternal high-fat diet (mHFD) consumption on offspring skeletal muscle physiology and exercise performance. We could show that maternal high-fat diet during gestation and lactation decreases the offspring’s training efficiency and endurance performance by influencing the epigenetic profile of their skeletal muscle and altering the adaptation to an acute exercise bout, which in long-term, increases offspring obesity susceptibility.
Experimental setup: To investigate this issue in detail, we conducted several studies with a similar maternal feeding regime. Dams (C57BL/6J) were either fed a low-fat diet (LFD; 10 energy% from fat) or high-fat diet (HFD; 40 energy% from fat) during pregnancy and lactation. After weaning, male offspring of both maternal groups were switched to a LFD, on which they remained until sacrifice in week 6, 15 or 25. In one study, LFD feeding was followed by HFD provision from week 15 until week 25 to elucidate the effects on offspring obesity susceptibility. In week 7, all mice were randomly allocated to a sedentary group (without running wheel) or an exercised group (with running wheel for voluntary exercise training). Additionally, treadmill endurance tests were conducted to investigate training performance and efficiency. In order to uncover regulatory mechanisms, each study was combined with a specific analytical setup, such as whole genome microarray analysis, gene and protein expression analysis, DNA methylation analyses, and enzyme activity assays.
Results: mHFD offspring displayed a reduced training efficiency and endurance capacity. This was not due to an altered skeletal muscle phenotype with changes in fiber size, number, and type. DNA methylation measurements in 6 week old offspring showed a hypomethylation of the Nr4a1 gene in mHFD offspring leading to an increased gene expression. Since Nr4a1 plays an important role in the regulation of skeletal muscle energy metabolism and early exercise adaptation, this could affect offspring training efficiency and exercise performance in later life.
Investigation of the acute response to exercise showed that mHFD offspring displayed a reduced gene expression of vascularization markers (Hif1a, Vegfb, etc) pointing towards a reduced angiogenesis which could possibly contribute to their reduced endurance capacity. Furthermore, an impaired glucose utilization of skeletal muscle during the acute exercise bout by an impaired skeletal muscle glucose handling was evidenced by higher blood glucose levels, lower GLUT4 translocation and diminished Lactate dehydrogenase activity in mHFD offspring immediately after the endurance test. These points towards a disturbed use of glucose as a substrate during endurance exercise. Prolonged HFD feeding during adulthood increases offspring fat mass gain in mHFD offspring compared to offspring from low-fat fed mothers and also reduces their insulin sensitivity pointing towards a higher obesity and diabetes susceptibility despite exercise training. Consequently, mHFD reduces offspring responsiveness to the beneficial effects of voluntary exercise training.
Conclusion: The results of this PhD thesis demonstrate that mHFD consumption impairs the offspring’s training efficiency and endurance capacity, and reduced the beneficial effects of exercise on the development of diet-induced obesity and insulin resistance in the offspring.
This might be due to changes in skeletal muscle epigenetic profile and/or an impaired skeletal muscle angiogenesis and glucose utilization during an acute exercise bout, which could contribute to a disturbed adaptive response to exercise training.
Ziel der vorliegenden Arbeit war die Synthese und Charakterisierung von anisotropen Goldnanopartikeln in einer geeigneten Polyelektrolyt-modifizierten Templatphase. Der Mittelpunkt bildet dabei die Auswahl einer geeigneten Templatphase, zur Synthese von einheitlichen und reproduzierbaren anisotropen Goldnanopartikeln mit den daraus resultierenden besonderen Eigenschaften. Bei der Synthese der anisotropen Goldnanopartikeln lag der Fokus in der Verwendung von Vesikeln als Templatphase, wobei hier der Einfluss unterschiedlicher strukturbildender Polymere (stark alternierende Maleamid-Copolymere PalH, PalPh, PalPhCarb und PalPhBisCarb mit verschiedener Konformation) und Tenside (SDS, AOT – anionische Tenside) bei verschiedenen Synthese- und Abtrennungsbedingungen untersucht werden sollte.
Im ersten Teil der Arbeit konnte gezeigt werden, dass PalPhBisCarb bei einem pH-Wert von 9 die Bedingungen eines Röhrenbildners für eine morphologische Transformation von einer vesikulären Phase in eine röhrenförmige Netzwerkstruktur erfüllt und somit als Templatphase zur formgesteuerten Bildung von Nanopartikeln genutzt werden kann.
Im zweiten Teil der Arbeit wurde dargelegt, dass die Templatphase PalPhBisCarb (pH-Wert von 9, Konzentration von 0,01 wt.%) mit AOT als Tensid und PL90G als Phospholipid (im Verhältnis 1:1) die effektivste Wahl einer Templatphase für die Bildung von anisotropen Strukturen in einem einstufigen Prozess darstellt. Bei einer konstanten Synthesetemperatur von 45 °C wurden die besten Ergebnisse bei einer Goldchloridkonzentration von 2 mM, einem Gold-Templat-Verhältnis von 3:1 und einer Synthesezeit von 30 Minuten erzielt. Ausbeute an anisotropen Strukturen lag bei 52 % (Anteil an dreieckigen Nanoplättchen von 19 %). Durch Erhöhung der Synthesetemperatur konnte die Ausbeute auf 56 % (29 %) erhöht werden.
Im dritten Teil konnte durch zeitabhängige Untersuchungen gezeigt werden, dass bei Vorhandensein von PalPhBisCarb die Bildung der energetisch nicht bevorzugten Plättchen-Strukturen bei Raumtemperatur initiiert wird und bei 45 °C ein Optimum annimmt.
Kintetische Untersuchungen haben gezeigt, dass die Bildung dreieckiger Nanoplättchen bei schrittweiser Zugabe der Goldchlorid-Präkursorlösung zur PalPhBisCarb enthaltenden Templatphase durch die Dosierrate der vesikulären Templatphase gesteuert werden kann. In umgekehrter Weise findet bei Zugabe der Templatphase zur Goldchlorid-Präkursorlösung bei 45 °C ein ähnlicher, kinetisch gesteuerter Prozess der Bildung von Nanodreiecken statt mit einer maximalen Ausbeute dreieckigen Nanoplättchen von 29 %.
Im letzten Kapitel erfolgten erste Versuche zur Abtrennung dreieckiger Nanoplättchen von den übrigen Geometrien der gemischten Nanopartikellösung mittels tensidinduzierter Verarmungsfällung. Bei Verwendung von AOT mit einer Konzentration von 0,015 M wurde eine Ausbeute an Nanoplättchen von 99 %, wovon 72 % dreieckiger Geometrien hatten, erreicht.
Die Elektrosprayionisation (ESI) ist eine der weitverbreitetsten Ionisationstechniken für flüssige Pro-ben in der Massen- und Ionenmobilitäts(IM)-Spektrometrie. Aufgrund ihrer schonenden Ionisierung wird ESI vorwiegend für empfindliche, komplexe Moleküle in der Biologie und Medizin eingesetzt. Überdies ist sie allerdings für ein sehr breites Spektrum an Substanzklassen anwendbar. Die IM-Spektrometrie wurde ursprünglich zur Detektion gasförmiger Proben entwickelt, die hauptsächlich durch radioaktive Quellen ionisiert werden. Sie ist die einzige analytische Methode, bei der Isomere in Echtzeit getrennt und über ihre charakteristische IM direkt identifiziert werden können. ESI wurde in den 90ger Jahren durch die Hill Gruppe in die IM-Spektrometrie eingeführt. Die Kombination wird bisher jedoch nur von wenigen Gruppen verwendet und hat deshalb noch ein hohes Entwick-lungspotential. Ein vielversprechendes Anwendungsfeld ist der Einsatz in der Hochleistungs-flüssigkeitschromatographie (HPLC) zur mehrdimensionalen Trennung. Heutzutage ist die HPLC die Standardmethode zur Trennung komplexer Proben in der Routineanalytik. HPLC-Trennungsgänge sind jedoch häufig langwierig und der Einsatz verschiedener Laufmittel, hoher Flussraten, von Puffern, sowie Laufmittelgradienten stellt hohe Anforderungen an die Detektoren. Die ESI-IM-Spektrometrie wurde in einigen Studien bereits als HPLC-Detektor eingesetzt, war dort bisher jedoch auf Flussratensplitting oder geringe Flussraten des Laufmittels beschränkt.
In dieser kumulativen Doktorarbeit konnte daher erstmals ein ESI IM-Spektrometer als HPLC-Detektor für den Flussratenbereich von 200-1500 μl/min entwickelt werden. Anhand von fünf Publi-kationen wurden (1) über eine umfassende Charakterisierung die Eignung des Spektrometers als HPLC-Detektor festgestellt, (2) ausgewählte komplexe Trenngänge präsentiert und (3) die Anwen-dung zum Reaktionsmonitoring und (4, 5) mögliche Weiterentwicklungen gezeigt.
Erfolgreich konnten mit dem selbst-entwickelten ESI IM-Spektrometer typische HPLC-Bedingungen wie Wassergehalte im Laufmittel von bis zu 90%, Pufferkonzentrationen von bis zu 10 mM, sowie Nachweisgrenzen von bis zu 50 nM erreicht werden. Weiterhin wurde anhand der komplexen Trennungsgänge (24 Pestizide/18 Aminosäuren) gezeigt, dass die HPLC und die IM-Spektrometrie eine hohe Orthogonalität besitzen. Eine effektive Peakkapazität von 240 wurde so realisiert. Auf der HPLC-Säule koeluierende Substanzen konnten über die Driftzeit getrennt und über ihre IM identifi-ziert werden, sodass die Gesamttrennzeiten erheblich minimiert werden konnten. Die Anwend-barkeit des ESI IM-Spektrometers zur Überwachung chemischer Synthesen wurde anhand einer dreistufigen Reaktion demonstriert. Es konnten die wichtigsten Edukte, Zwischenprodukte und Produkte aller Stufen identifiziert werden. Eine quantitative Auswertung war sowohl über eine kurze HPLC-Vortrennung als auch durch die Entwicklung eines eigenen Kalibrierverfahrens, welches die Ladungskonkurrenz bei ESI berücksichtigt, ohne HPLC möglich. Im zweiten Teil der Arbeit werden zwei Weiterentwicklungen des Spektrometers präsentiert. Eine Möglichkeit ist die Reduzierung des Drucks in den intermediären Bereich (300 - 1000 mbar) mit dem Ziel der Verringerung der benötigten Spannungen. Mithilfe von Streulichtbildern und Strom-Spannungs-Kurven wurden für geringe Drücke eine verminderte Freisetzung der Analyt-Ionen aus den Tropfen festgestellt. Die Verluste konnten jedoch über höhere elektrische Feldstärken ausgeglichen werden, sodass gleiche Nachweisgrenzen bei 500 mbar und bei 1 bar erreicht wurden. Die zweite Weiterentwicklung ist ein neuartiges Ionentors mit Pulsschaltung, welches eine Verdopplung der Auflösung auf bis zu R > 100 bei gleicher Sensitivität ermöglichte. Eine denkbare Anwendung im Bereich der Peptidanalytik wurde mit beachtlichen Auflösungen der Peptide von R = 90 gezeigt.
The motivation of this work was to investigate the self-assembly of a block copolymer species that attended little attraction before, double hydrophilic block copolymers (DHBCs). DHBCs consist of two linear hydrophilic polymer blocks. The self-assembly of DHBCs towards suprastructures such as particles and vesicles is determined via a strong difference in hydrophilicity between the corresponding blocks leading to a microphase separation due to immiscibility. The benefits of DHBCs and the corresponding particles and vesicles, such as biocompatibility, high permeability towards water and hydrophilic compounds as well as the large amount of possible functionalizations that can be addressed to the block copolymers make the application of DHBC based structures a viable choice in biomedicine. In order to assess a route towards self-assembled structures from DHBCs that display the potential to act as cargos for future applications, several block copolymers containing two hydrophilic polymer blocks were synthesized. Poly(ethylene oxide)-b-poly(N-vinylpyrrolidone) (PEO-b-PVP) and Poly(ethylene oxide)-b-poly(N-vinylpyrrolidone-co-N-vinylimidazole) (PEO-b-P(VP-co-VIm) block copolymers were synthesized via reversible deactivation radical polymerization (RDRP) techniques starting from a PEO-macro chain transfer agent. The block copolymers displayed a concentration dependent self-assembly behavior in water which was determined via dynamic light scattering (DLS). It was possible to observe spherical particles via laser scanning confocal microscopy (LSCM) and cryogenic scanning electron microscopy (cryo SEM) at highly concentrated solutions of PEO-b-PVP. Furthermore, a crosslinking strategy with (PEO-b-P(VP-co-VIm) was developed applying a diiodo derived crosslinker diethylene glycol bis(2-iodoethyl) ether to form quaternary amines at the VIm units. The formed crosslinked structures proved stability upon dilution and transfer into organic solvents. Moreover, self-assembly and crosslinking in DMF proved to be more advantageous and the crosslinked structures could be successfully transferred to aqueous solution. The afforded spherical submicron particles could be visualized via LSCM, cryo SEM and Cryo TEM.
Double hydrophilic pullulan-b-poly(acrylamide) block copolymers were synthesized via copper catalyzed alkyne azide cycloaddition (CuAAC) starting from suitable pullulan alkyne and azide functionalized poly(N,N-dimethylacrylamide) (PDMA) and poly(N-ethylacrylamide) (PEA) homopolymers. The conjugation reaction was confirmed via SEC and 1H-NMR measurements. The self-assembly of the block copolymers was monitored with DLS and static light scattering (SLS) measurements indicating the presence of hollow spherical structures. Cryo SEM measurements could confirm the presence of vesicular structures for Pull-b-PEA block copolymers. Solutions of Pull-b-PDMA displayed particles in cryo SEM. Moreover, an end group functionalization of Pull-b-PDMA with Rhodamine B allowed assessing the structure via LSCM and hollow spherical structures were observed indicating the presence of vesicles, too.
An exemplified pathway towards a DHBC based drug delivery vehicle was demonstrated with the block copolymer Pull-b-PVP. The block copolymer was synthesized via RAFT/MADIX techniques starting from a pullulan chain transfer agent. Pull-b-PVP displayed a concentration dependent self-assembly in water with an efficiency superior to the PEO-b-PVP system, which could be observed via DLS. Cryo SEM and LSCM microscopy displayed the presence of spherical structures. In order to apply a reversible crosslinking strategy on the synthesized block copolymer, the pullulan block was selectively oxidized to dialdehydes with NaIO4. The oxidation of the block copolymer was confirmed via SEC and 1H-NMR measurements. The self-assembled and oxidized structures were subsequently crosslinked with cystamine dihiydrochloride, a pH and redox responsive crosslinker resulting in crosslinked vesicles which were observed via cryo SEM. The vesicular structures of crosslinked Pull-b-PVP could be disassembled by acid treatment or the application of the redox agent tris(2-carboxyethyl)-phosphin-hydrochloride. The successful disassembly was monitored with DLS measurements.
To conclude, self-assembled structures from DHBCs such as particles and vesicles display a strong potential to generate an impact on biomedicine and nanotechnologies. The variety of DHBC compositions and functionalities are very promising features for future applications.
Recognizing, understanding, and responding to quantities are considerable skills for human beings. We can easily communicate quantities, and we are extremely efficient in adapting our behavior to numerical related tasks. One usual task is to compare quantities. We also use symbols like digits in numerical-related tasks. To solve tasks including digits, we must to rely on our previously learned internal number representations.
This thesis elaborates on the process of number comparison with the use of noisy mental representations of numbers, the interaction of number and size representations and how we use mental number representations strategically. For this, three studies were carried out.
In the first study, participants had to decide which of two presented digits was numerically larger. They had to respond with a saccade in the direction of the anticipated answer. Using only a small set of meaningfully interpretable parameters, a variant of random walk models is described that accounts for response time, error rate, and variance of response time for the full matrix of 72 digit pairs. In addition, the used random walk model predicts a numerical distance effect even for error response times and this effect clearly occurs in the observed data. In relation to corresponding correct answers error responses were systematically faster. However, different from standard assumptions often made in random walk models, this account required that the distributions of step sizes of the induced random walks be asymmetric to account for this asymmetry between correct and incorrect responses.
Furthermore, the presented model provides a well-defined framework to investigate the nature and scale (e.g., linear vs. logarithmic) of the mapping of numerical magnitude onto its internal representation. In comparison of the fits of proposed models with linear and logarithmic mapping, the logarithmic mapping is suggested to be prioritized.
Finally, we discuss how our findings can help interpret complex findings (e.g., conflicting speed vs. accuracy trends) in applied studies that use number comparison as a well-established diagnostic tool. Furthermore, a novel oculomotoric effect is reported, namely the saccadic overschoot effect. The participants responded by saccadic eye movements and the amplitude of these saccadic responses decreases with numerical distance.
For the second study, an experimental design was developed that allows us to apply the signal detection theory to a task where participants had to decide whether a presented digit was physically smaller or larger. A remaining question is, whether the benefit in (numerical magnitude – physical size) congruent conditions is related to a better perception than in incongruent conditions. Alternatively, the number-size congruency effect is mediated by response biases due to numbers magnitude. The signal detection theory is a perfect tool to distinguish between these two alternatives. It describes two parameters, namely sensitivity and response bias. Changes in the sensitivity are related to the actual task performance due to real differences in perception processes whereas changes in the response bias simply reflect strategic implications as a stronger preparation (activation) of an anticipated answer. Our results clearly demonstrate that the number-size congruency effect cannot be reduced to mere response bias effects, and that genuine sensitivity gains for congruent number-size pairings contribute to the number-size congruency effect.
Third, participants had to perform a SNARC task – deciding whether a presented digit was odd or even. Local transition probability of irrelevant attributes (magnitude) was varied while local transition probability of relevant attributes (parity) and global probability occurrence of each stimulus were kept constantly. Participants were quite sensitive in recognizing the underlying local transition probability of irrelevant attributes. A gain in performance was observed for actual repetitions of the irrelevant attribute in relation to changes of the irrelevant attribute in high repetition conditions compared to low repetition conditions. One interpretation of these findings is that information about the irrelevant attribute (magnitude) in the previous trial is used as an informative precue, so that participants can prepare early processing stages in the current trial, with the corresponding benefits and costs typical of standard cueing studies.
Finally, the results reported in this thesis are discussed in relation to recent studies in numerical cognition.
Aufgrund verschiedener wissenschaftlicher Erkenntnisse wird jungen Sporttreibenden vom Gebrauch von Nahrungsergänzungsmitteln (NEM) abgeraten. Diese Dissertation verfolgt vor dem Hintergrund der Theorie der Zielsysteme (TDZ) das Ziel der Erstellung anwendungsorientieren Handlungswissens, anhand dessen Interventionsempfehlungen zur Reduzierung des prävalenten NEM-Konsums im Nachwuchssport ableitbar sind. Insgesamt wurden sechs Untersuchungen durchgeführt. Die Versuchsteilnehmenden absolvierten in sämtlichen Studien eine Variante der lexikalischen Entscheidungsaufgabe. Diese Aufgabe diente der Operationalisierung von automatisch aktivier- und abrufbaren nahrungsergänzungsmittelbezogenen Ziel-Mittel-Relationen.
In einer Stichprobe von Sportstudierenden zeigte sich, dass NEM mit dem Ziel Leistung assoziiert sind (Studie 1). Unter Berücksichtigung des NEM-Konsums wurde dieses Ergebnis für Nachwuchsathletinnen und -athleten aus dem Breitensport repliziert (Studie 2). Zusätzlich konnte in beiden Studien die Bedeutung dieser Ziel-Mittel-Relationen für das Verhalten nachgewiesen werden. In den nachfolgenden Untersuchungen wurden spezifische Veränderungsmechanismen der verhaltensleitenden Ziel-Mittel-Relation aus Leistung und NEM zunächst an Sportstudierenden experimentell evaluiert. Durch das Herausstellen der fehlenden leistungssteigernden Wirkung von NEM konnte diese Zielassoziation nicht modifiziert werden (Studie 3). Das Betonen gesundheitsschädigender Konsequenzen (Studie 4) und das Akzentuieren einer gesunden Ernährung (Studie 5) erwiesen sich demgegenüber als geeignet zur Veränderung der Ziel-Mittel-Relation. Das Herausstellen einer gesunden Ernährung führte deskriptiv bei Nachwuchsathletinnen und -athleten ebenfalls zur Modifikation der Zielassoziation (Studie 6). Die inferenzstatistische Bestätigung der Ergebnisse dieser Studie steht aufgrund der geringen Teststärke der Untersuchung noch aus.
Insgesamt verdeutlichen die Ergebnisse, dass die auf Ebene automatischer Kognitionen bestehende und verhaltensleitende Assoziation des Gebrauchs von NEM mit Leistung durch die Akzentuierung gesundheitlicher Perspektiven experimentell verändert werden kann. Abschließend wird die theoretische und praktische Bedeutung des erstellten Handlungswissen für künftige Interventionsempfehlungen zur Reduzierung des Gebrauchs von NEM diskutiert.
In this era of high-speed informatization and globalization, online education is no longer an exquisite concept in the ivory tower, but a rapidly developing industry closely relevant to people's daily lives. Numerous lectures are recorded in form of multimedia data, uploaded to the Internet and made publicly accessible from anywhere in this world. These lectures are generally addressed as e-lectures. In recent year, a new popular form of e-lectures, the Massive Open Online Courses (MOOCs), boosts the growth of online education industry and somehow turns "learning online" into a fashion.
As an e-learning provider, besides to keep improving the quality of e-lecture content, to provide better learning environment for online learners is also a highly important task. This task can be preceded in various ways, and one of them is to enhance and upgrade the learning materials provided: e-lectures could be more than videos. Moreover, this process of enhancement or upgrading should be done automatically, without giving extra burdens to the lecturers or teaching teams, and this is the aim of this thesis.
The first part of this thesis is an integrated framework of multi-lingual subtitles production, which can help online learners penetrate the language barrier. The framework consists of Automatic Speech Recognition (ASR), Sentence Boundary Detection (SBD) and Machine Translation (MT), among which the proposed SBD solution is major technical contribution, building on Deep Neural Network (DNN) and Word Vector (WV) and achieving state-of-the-art performance. Besides, a quantitative evaluation with dozens of volunteers is also introduced to measure how these auto-generated subtitles could actually help in context of e-lectures.
Secondly, a technical solution "TOG" (Tree-Structure Outline Generation) is proposed to extract textual content from the displaying slides recorded in video and re-organize them into a hierarchical lecture outline, which may serve in multiple functions, such like preview, navigation and retrieval. TOG runs adaptively and can be roughly divided into intra-slide and inter-slides phases. Table detection and lecture video segmentation can be implemented as sub- or post-application in these two phases respectively. Evaluation on diverse e-lectures shows that all the outlines, tables and segments achieved are trustworthily accurate.
Based on the subtitles and outlines previously created, lecture videos can be further split into sentence units and slide-based segment units. A lecture highlighting process is further applied on these units, in order to capture and mark the most important parts within the corresponding lecture, just as what people do with a pen when reading paper books. Sentence-level highlighting depends on the acoustic analysis on the audio track, while segment-level highlighting focuses on exploring clues from the statistical information of related transcripts and slide content. Both objective and subjective evaluations prove that the proposed lecture highlighting solution is with decent precision and welcomed by users.
All above enhanced e-lecture materials have been already implemented in actual use or made available for implementation by convenient interfaces.
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.
BACKGROUND: Aggressive behavior at an early age is linked to a broad range of psychosocial problems in later life. That is why risk factors of the occurrence and the development of aggression have been examined for a long time in psychological science. The present doctoral dissertation aims to expand this research by investigating risk factors in three intrapersonal domains using the prominent social-information processing approach by Crick and Dodge (1994) as a framework model. Anger regulation was examined as an affective, theory of mind as a cognitive, and physical attractiveness as an appearance-related developmental factor of aggression in middle childhood. An additional goal of this work was to develop and validate a behavioral observation assessment of anger regulation as past research lacked in ecologically valid measures of anger regulation that are applicable for longitudinal studies.
METHODS: Three empirical studies address the aforementioned intrapersonal risk factors. In each study, data from the PIER-project were used, a three-wave-longitudinal study covering three years with a total sample size of 1,657 children in the age between 6 and 11 years (at the first measurement point). The central constructs were assessed via teacher-reports (aggression), behavioral observation (anger regulation), computer tests (theory of mind), and independent ratings (physical attractiveness). The predictive value of each proposed risk factor for the development of aggressive behavior was examined via structural equation modeling.
RESULTS AND CONCLUSION: The newly developed behavioral observation measure was found to be a reliable and valid tool to assess anger regulation in middle childhood, but limited in capturing a full range of relevant regulation strategies. That might be the reason, why maladaptive anger regulation was not found to function as a risk factor of subsequent aggressive behavior. However, children’s deficits in theory of mind and a low level in physical attractiveness significantly predicted later aggression. Problematic peer relationships were identified as underlying the link between low attractiveness and aggression. Thus, fostering children’s skills in theory of mind and their ability to call existing beliefs about the nature of more versus less attractive individuals into question may be important starting points for the prevention of aggressive behavior in middle childhood.
Functional nanoporous carbon-based materials derived from oxocarbon-metal coordination complexes
(2017)
Nanoporous carbon based materials are of particular interest for both science and industry due to their exceptional properties such as a large surface area, high pore volume, high electroconductivity as well as high chemical and thermal stability. Benefiting from these advantageous properties, nanoporous carbons proved to be useful in various energy and environment related applications including energy storage and conversion, catalysis, gas sorption and separation technologies. The synthesis of nanoporous carbons classically involves thermal carbonization of the carbon precursors (e.g. phenolic resins, polyacrylonitrile, poly(vinyl alcohol) etc.) followed by an activation step and/or it makes use of classical hard or soft templates to obtain well-defined porous structures. However, these synthesis strategies are complicated and costly; and make use of hazardous chemicals, hindering their application for large-scale production. Furthermore, control over the carbon materials properties is challenging owing to the relatively unpredictable processes at the high carbonization temperatures.
In the present thesis, nanoporous carbon based materials are prepared by the direct heat treatment of crystalline precursor materials with pre-defined properties. This synthesis strategy does not require any additional carbon sources or classical hard- or soft templates. The highly stable and porous crystalline precursors are based on coordination compounds of the squarate and croconate ions with various divalent metal ions including Zn2+, Cu2+, Ni2+, and Co2+, respectively. Here, the structural properties of the crystals can be controlled by the choice of appropriate synthesis conditions such as the crystal aging temperature, the ligand/metal molar ratio, the metal ion, and the organic ligand system. In this context, the coordination of the squarate ions to Zn2+ yields porous 3D cube crystalline particles. The morphology of the cubes can be tuned from densely packed cubes with a smooth surface to cubes with intriguing micrometer-sized openings and voids which evolve on the centers of the low index faces as the crystal aging temperature is raised. By varying the molar ratio, the particle shape can be changed from truncated cubes to perfect cubes with right-angled edges.
These crystalline precursors can be easily transformed into the respective carbon based materials by heat treatment at elevated temperatures in a nitrogen atmosphere followed by a facile washing step. The resulting carbons are obtained in good yields and possess a hierarchical pore structure with well-organized and interconnected micro-, meso- and macropores. Moreover, high surface areas and large pore volumes of up to 1957 m2 g-1 and 2.31 cm3 g-1 are achieved, respectively, whereby the macroscopic structure of the precursors is preserved throughout the whole synthesis procedure.
Owing to these advantageous properties, the resulting carbon based materials represent promising supercapacitor electrode materials for energy storage applications. This is exemplarily demonstrated by employing the 3D hierarchical porous carbon cubes derived from squarate-zinc coordination compounds as electrode material showing a specific capacitance of 133 F g-1 in H2SO4 at a scan rate of 5 mV s-1 and retaining 67% of this specific capacitance when the scan rate is increased to 200 mV s-1.
In a further application, the porous carbon cubes derived from squarate-zinc coordination compounds are used as high surface area support material and decorated with nickel nanoparticles via an incipient wetness impregnation. The resulting composite material combines a high surface area, a hierarchical pore structure with high functionality and well-accessible pores. Moreover, owing to their regular micro-cube shape, they allow for a good packing of a fixed-bed flow reactor along with high column efficiency and a minimized pressure drop throughout the packed reactor. Therefore, the composite is employed as heterogeneous catalyst in the selective hydrogenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran showing good catalytic performance and overcoming the conventional problem of column blocking.
Thinking about the rational design of 3D carbon geometries, the functions and properties of the resulting carbon-based materials can be further expanded by the rational introduction of heteroatoms (e.g. N, B, S, P, etc.) into the carbon structures in order to alter properties such as wettability, surface polarity as well as the electrochemical landscape. In this context, the use of crystalline materials based on oxocarbon-metal ion complexes can open a platform of highly functional materials for all processes that involve surface processes.
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.
In the wake of 21st century, humanity witnessed a phenomenal raise of urban agglomerations as powerhouses for innovation and socioeconomic growth. Driving much of national (and in few instances even global) economy, such a gargantuan raise of cities is also accompanied by subsequent increase in energy, resource consumption and waste generation. Much of anthropogenic transformation of Earth's environment in terms of environmental pollution at local level to planetary scale in the form of climate change is currently taking place in cities. Projected to be crucibles for entire humanity by the end of this century, the ultimate fate of humanity predominantly lies in the hands of technological innovation, urbanites' attitudes towards energy/resource consumption and development pathways undertaken by current and future cities. Considering the unparalleled energy, resource consumption and emissions currently attributed to global cities, this thesis addresses these issues from an efficiency point of view. More specifically, this thesis addresses the influence of population size, density, economic geography and technology in improving urban greenhouse gas (GHG) emission efficiency and identifies the factors leading to improved eco-efficiency in cities. In order to investigate the in uence of these factors in improving emission and resource efficiency in cities, a multitude of freely available datasets were coupled with some novel methodologies and analytical approaches in this thesis.
Merging the well-established Kaya Identity to the recently developed urban scaling laws, an Urban Kaya Relation is developed to identify whether large cities are more emission efficient and the intrinsic factors leading to such (in)efficiency. Applying Urban Kaya Relation to a global dataset of 61 cities in 12 countries, this thesis identifed that large cities in developed regions of the world will bring emission efficiency gains because of the better technologies implemented in these cities to produce and utilize energy consumption while the opposite is the case for cities in developing regions. Large cities in developing countries are less efficient mainly because of their affluence and lack of efficient technologies. Apart from the in uence of population size on emission efficiency, this thesis identified the crucial role played by population density in improving building and on-road transport sector related emission efficiency in cities. This is achieved by applying the City Clustering Algorithm (CCA) on two different gridded land use datasets and a standard emission inventory to attribute these sectoral emissions to all inhabited settlements in the USA. Results show that doubling the population density would entail a reduction in the total CO2 emissions in buildings and on-road sectors typically by at least 42 %. Irrespective of their population size and density, cities are often blamed for their intensive resource consumption that threatens not only local but also global sustainability. This thesis merged the concept of urban metabolism with benchmarking and identified cities which are eco-efficient. These cities enable better socioeconomic conditions while being less burden to the environment. Three environmental burden indicators (annual average NO2 concentration, per capita waste generation and water consumption) and two socioeconomic indicators (GDP per capita and employment ratio) for 88 most populous European cities are considered in this study. Using two different non-parametric ranking methods namely regression residual ranking and Data Envelopment Analysis (DEA), eco-efficient cities and their determining factors are identified. This in-depth analysis revealed that mature cities with well-established economic structures such as Munich, Stockholm and Oslo are eco-efficient. Further, correlations between objective eco-efficiency ranking with each of the indicator rankings and the ranking of urbanites' subjective perception about quality of life are analyzed. This analysis revealed that urbanites' perception about quality of life is not merely confined to the socioeconomic well-being but rather to their combination with lower environmental burden.
In summary, the findings of this dissertation has three general conclusions for improving emission and ecological efficiency in cities. Firstly, large cities in emerging nations face a huge challenge with respect to improving their emission efficiency. The task in front of these cities is threefold: (1) deploying efficient technologies for the generation of electricity and improvement of public transportation to unlock their leap frogging potential, (2) addressing the issue of energy poverty and (3) ensuring that these cities do not develop similar energy consumption patterns with infrastructure lock-in behavior similar to those of cities in developed regions. Secondly, the on-going urban sprawl as a global phenomenon will decrease the emission efficiency within the building and transportation sector. Therefore, local policy makers should identify adequate fiscal and land use policies to curb urban sprawl. Lastly, since mature cities with well-established economic structures are more eco-efficient and urbanites' perception re ects its combination with decreasing environmental burden; there is a need to adopt and implement strategies which enable socioeconomic growth in cities whilst decreasing their environment burden.
Lithospheric plates move over the low viscosity asthenosphere balancing several forces. The driving forces include basal shear stress exerted by mantle convection and plate boundary forces such as slab pull and ridge push, whereas the resisting forces include inter-plate friction, trench resistance, and cratonic root resistance. These generate plate motions, the lithospheric stress field and dynamic topography which are observed with different geophysical methods. The orientation and tectonic regime of the observed crustal/lithospheric stress field further contribute to our knowledge of different deformation processes occurring within the Earth's crust and lithosphere. Using numerical models previous studies were able to identify major forces generating stresses in the crust and lithosphere which also contribute to the formation of topography as well as driving lithospheric plates. They showed that the first-order stress pattern explaining about 80\,\% of the stress field originates from a balance of forces acting at the base of the moving lithospheric plates due to convective flow in the underlying mantle. The remaining second-order stress pattern is due to lateral density variations in the crust and lithosphere in regions of pronounced topography and high gravitational potential, such as the Himalayas and mid-ocean ridges. By linking global lithosphere dynamics to deep mantle flow this study seeks to evaluate the influence of shallow and deep density heterogenities on plate motions, lithospheric stress field and dynamic topography using the geoid as a major constraint for mantle rheology. We use the global 3D lithosphere-asthenosphere model SLIM3D with visco-elasto-plastic rheology coupled at 300 km depth to a spectral model of mantle flow. The complexity of the lithosphere-asthenosphere component allows for the simulation of power-law rheology with creep parameters accounting for both diffusion and dislocation creep within the uppermost 300 km.
First we investigate the influence of intra-plate friction and asthenospheric viscosity on present-day plate motions. Previous modelling studies have suggested that small friction coefficients (µ < 0.1, yield stress ~ 100 MPa) can lead to plate tectonics in models of mantle convection. Here we show that, in order to match present-day plate motions and net rotation, the frictional parameter must be less than 0.05. We are able to obtain a good fit with the magnitude and orientation of observed plate velocities (NUVEL-1A) in a no-net-rotation (NNR) reference frame with µ < 0.04 and minimum asthenosphere viscosity ~ 5*10e19 Pas to 10e20 Pas. Our estimates of net rotation (NR) of the lithosphere suggest that amplitudes ~ 0.1-0.2 °/Ma, similar to most observation-based estimates, can be obtained with asthenosphere viscosity cutoff values of ~ 10e19 Pas to 5*10e19 Pas and friction coefficient µ < 0.05.
The second part of the study investigates further constraints on shallow and deep mantle heterogeneities causing plate motion by predicting lithosphere stress field and topography and validating with observations. Lithosphere stresses and dynamic topography are computed using the modelling setup and rheological parameters for prescribed plate motions. We validate our results with the World Stress Map 2016 (WSM2016) and the observed residual topography. Here we tested a number of upper mantle thermal-density structures. The one used to calculate plate motions is considered the reference thermal-density structure. This model is derived from a heat flow model combined with a sea floor age model. In addition we used three different thermal-density structures derived from global S-wave velocity models to show the influence of lateral density heterogeneities in the upper 300 km on model predictions. A large portion of the total dynamic force generating stresses in the crust/lithosphere has its origin in the deep mantle, while topography is largely influenced by shallow heterogeneities. For example, there is hardly any difference between the stress orientation patterns predicted with and without consideration of the heterogeneities in the upper mantle density structure across North America, Australia, and North Africa. However, the crust is dominant in areas of high altitude for the stress orientation compared to the all deep mantle contribution.
This study explores the sensitivity of all the considered surface observables with regards to model parameters providing insights into the influence of the asthenosphere and plate boundary rheology on plate motion as we test various thermal-density structures to predict stresses and topography.
This cumulative dissertation consists of five chapters. In terms of research content, my thesis can be divided into two parts. Part one examines local interactions and spillover effects between small regional governments using spatial econometric methods. The second part focuses on patterns within municipalities and inspects which institutions of citizen participation, elections and local petitions, influence local housing policies.
The central aim of this thesis is to demonstrate the benefits of innovative frequency-based methods to better explain the variability observed in lake ecosystems. Freshwater ecosystems may be the most threatened part of the hydrosphere. Lake ecosystems are particularly sensitive to changes in climate and land use because they integrate disturbances across their entire catchment. This makes understanding the dynamics of lake ecosystems an intriguing and important research priority. This thesis adds new findings to the baseline knowledge regarding variability in lake ecosystems. It provides a literature-based, data-driven and methodological framework for the investigation of variability and patterns in environmental parameters in the time frequency domain.
Observational data often show considerable variability in the environmental parameters of lake ecosystems. This variability is mostly driven by a plethora of periodic and stochastic processes inside and outside the ecosystems. These run in parallel and may operate at vastly different time scales, ranging from seconds to decades. In measured data, all of these signals are superimposed, and dominant processes may obscure the signals of other processes, particularly when analyzing mean values over long time scales. Dominant signals are often caused by phenomena at long time scales like seasonal cycles, and most of these are well understood in the limnological literature. The variability injected by biological, chemical and physical processes operating at smaller time scales is less well understood. However, variability affects the state and health of lake ecosystems at all time scales. Besides measuring time series at sufficiently high temporal resolution, the investigation of the full spectrum of variability requires innovative methods of analysis.
Analyzing observational data in the time frequency domain allows to identify variability at different time scales and facilitates their attribution to specific processes. The merit of this approach is subsequently demonstrated in three case studies. The first study uses a conceptual analysis to demonstrate the importance of time scales for the detection of ecosystem responses to climate change. These responses often occur during critical time windows in the year, may exhibit a time lag and can be driven by the exceedance of thresholds in their drivers. This can only be detected if the temporal resolution of the data is high enough. The second study applies Fast Fourier Transform spectral analysis to two decades of daily water temperature measurements to show how temporal and spatial scales of water temperature variability can serve as an indicator for mixing in a shallow, polymictic lake. The final study uses wavelet coherence as a diagnostic tool for limnology on a multivariate high-frequency data set recorded between the onset of ice cover and a cyanobacteria summer bloom in the year 2009 in a polymictic lake. Synchronicities among limnological and meteorological time series in narrow frequency bands were used to identify and disentangle prevailing limnological processes.
Beyond the novel empirical findings reported in the three case studies, this thesis aims to more generally be of interest to researchers dealing with now increasingly available time series data at high temporal resolution. A set of innovative methods to attribute patterns to processes, their drivers and constraints is provided to help make more efficient use of this kind of data.
Natural products and their derivatives have always been a source of drug leads. In particular, bacterial compounds have played an important role in drug development, for example in the field of antibiotics. A decrease in the discovery of novel leads from natural sources and the hope of finding new leads through the generation of large libraries of drug-like compounds by combinatorial chemistry aimed at specific molecular targets drove the pharmaceutical companies away from research on natural products. However, recent technological advances in genetics, bioinformatics and analytical chemistry have revived the interest in natural products. The ribosomally synthesized and post-translationally modified peptides (RiPPs) are a group of natural products generated by the action of post-translationally modifying enzymes on precursor peptides translated from mRNA by ribosomes. The great substrate promiscuity exhibited by many of the enzymes from RiPP biosynthetic pathways have led to the generation of hundreds of novel synthetic and semisynthetic variants, including variants carrying non-canonical amino acids (ncAAs). The microviridins are a family of RiPPs characterized by their atypical tricyclic structure composed of lactone and lactam rings, and their activity as serine protease inhibitors. The generalities of their biosynthetic pathway have already been described, however, the lack of information on details such as the protease responsible for cleaving off the leader peptide from the cyclic core peptide has impeded the fast and cheap production of novel microviridin variants. In the present work, knowledge on leader peptide activation of enzymes from other RiPP families has been extrapolated to the microviridin family, making it possible to bypass the need of a leader peptide. This feature allowed for the exploitation of the microviridin biosynthetic machinery for the production of novel variants through the establishment of an efficient one-pot in vitro platform. The relevance of this chemoenzymatic approach has been exemplified by the synthesis of novel potent serine protease inhibitors from both rationally-designed peptide libraries and bioinformatically predicted microviridins. Additionally, new structure-activity relationships (SARs) could be inferred by screening microviridin intermediates. The significance of this technique was further demonstrated by the simple incorporation of ncAAs into the microviridin scaffold.
Start-up incentives targeted at unemployed individuals have become an important tool of the Active Labor Market Policy (ALMP) to fight unemployment in many countries in recent years. In contrast to traditional ALMP instruments like training measures, wage subsidies, or job creation schemes, which are aimed at reintegrating unemployed individuals into dependent employment, start-up incentives are a fundamentally different approach to ALMP, in that they intend to encourage and help unemployed individuals to exit unemployment by entering self-employment and, thus, by creating their own jobs. In this sense, start-up incentives for unemployed individuals serve not only as employment and social policy to activate job seekers and combat unemployment but also as business policy to promote entrepreneurship. The corresponding empirical literature on this topic so far has been mainly focused on the individual labor market perspective, however. The main part of the thesis at hand examines the new start-up subsidy (“Gründungszuschuss”) in Germany and consists of four empirical analyses that extend the existing evidence on start-up incentives for unemployed individuals from multiple perspectives and in the following directions:
First, it provides the first impact evaluation of the new start-up subsidy in Germany. The results indicate that participation in the new start-up subsidy has significant positive and persistent effects on both reintegration into the labor market as well as the income profiles of participants, in line with previous evidence on comparable German and international programs, which emphasizes the general potential of start-up incentives as part of the broader ALMP toolset. Furthermore, a new innovative sensitivity analysis of the applied propensity score matching approach integrates findings from entrepreneurship and labor market research about the key role of an individual’s personality on start-up decision, business performance, as well as general labor market outcomes, into the impact evaluation of start-up incentives. The sensitivity analysis with regard to the inclusion and exclusion of usually unobserved personality variables reveals that differences in the estimated treatment effects are small in magnitude and mostly insignificant. Consequently, concerns about potential overestimation of treatment effects in previous evaluation studies of similar start-up incentives due to usually unobservable personality variables are less justified, as long as the set of observed control variables is sufficiently informative (Chapter 2).
Second, the thesis expands our knowledge about the longer-term business performance and potential of subsidized businesses arising from the start-up subsidy program. In absolute terms, the analysis shows that a relatively high share of subsidized founders successfully survives in the market with their original businesses in the medium to long run. The subsidy also yields a “double dividend” to a certain extent in terms of additional job creation. Compared to “regular”, i.e., non-subsidized new businesses founded by non-unemployed individuals in the same quarter, however, the economic and growth-related impulses set by participants of the subsidy program are only limited with regard to employment growth, innovation activity, or investment. Further investigations of possible reasons for these differences show that differential business growth paths of subsidized founders in the longer run seem to be mainly limited by higher restrictions to access capital and by unobserved factors, such as less growth-oriented business strategies and intentions, as well as lower (subjective) entrepreneurial persistence. Taken together, the program has only limited potential as a business and entrepreneurship policy intended to induce innovation and economic growth (Chapters 3 and 4).
And third, an empirical analysis on the level of German regional labor markets yields that there is a high regional variation in subsidized start-up activity relative to overall new business formation. The positive correlation between regular start-up intensity and the share among all unemployed individuals who participate in the start-up subsidy program suggests that (nascent) unemployed founders also profit from the beneficial effects of regional entrepreneurship capital. Moreover, the analysis of potential deadweight and displacement effects from an aggregated regional perspective emphasizes that the start-up subsidy for unemployed individuals represents a market intervention into existing markets, which affects incumbents and potentially produces inefficiencies and market distortions. This macro perspective deserves more attention and research in the future (Chapter 5).
In Germany more than 200.000 persons die of cancer every year, which makes it the second most common cause of death. Chemotherapy and radiation therapy are often combined to exploit a supra-additive effect, as some chemotherapeutic agents like halogenated nucleobases sensitize the cancerous tissue to radiation. The radiosensitizing action of certain therapeutic agents can be at least partly assigned to their interaction with secondary low energy electrons (LEEs) that are generated along the track of the ionizing radiation. In the therapy of cancer DNA is an important target, as severe DNA damage like double strand breaks induce the cell death. As there is only a limited number of radiosensitizing agents in clinical practice, which are often strongly cytotoxic, it would be beneficial to get a deeper understanding of the interaction of less toxic potential radiosensitizers with secondary reactive species like LEEs. Beyond that LEEs can be generated by laser illuminated nanoparticles that are applied in photothermal therapy (PTT) of cancer, which is an attempt to treat cancer by an increase of temperature in the cells. However, the application of halogenated nucleobases in PTT has not been taken into account so far. In this thesis the interaction of the potential radiosensitizer 8-bromoadenine (8BrA) with LEEs was studied. In a first step the dissociative electron attachment (DEA) in the gas phase was studied in a crossed electron-molecular beam setup. The main fragmentation pathway was revealed as the cleavage of the C-Br bond. The formation of a stable parent anion was observed for electron energies around 0 eV. Furthermore, DNA origami nanostructures were used as platformed to determine electron induced strand break cross sections of 8BrA sensitized oligonucleotides and the corresponding nonsensitized sequence as a function of the electron energy. In this way the influence of the DEA resonances observed for the free molecules on the DNA strand breaks was examined. As the surrounding medium influences the DEA, pulsed laser illuminated gold nanoparticles (AuNPs) were used as a nanoscale electron source in an aqueous environment. The dissociation of brominated and native nucleobases was tracked with UV-Vis absorption spectroscopy and the generated fragments were identified with surface enhanced Raman scattering (SERS). Beside the electron induced damage, nucleobase analogues are decomposed in the vicinity of the laser illuminatednanoparticles due to the high temperatures. In order to get a deeper understanding of the different dissociation mechanisms, the thermal decomposition of the nucleobases in these systems was studied and the influence of the adsorption kinetics of the molecules was elucidated. In addition to the pulsed laser experiments, a dissociative electron transfer from plasmonically generated ”hot electrons” to 8BrA was observed under low energy continuous wave laser illumination and tracked with SERS. The reaction was studied on AgNPs and AuNPs as a function of the laser intensity and wavelength. On dried samples the dissociation of the molecule was described by fractal like kinetics. In solution, the dissociative electron transfer was observed as well. It turned out that the timescale of the reaction rates were slightly below typical integration times of Raman spectra. In consequence such reactions need to be taken into account in the interpretation of SERS spectra of electrophilic molecules. The findings in this thesis help to understand the interaction of brominated nucleobases with plasmonically generated electrons and free electrons. This might help to evaluate the potential radiosensitizing action of such molecules in cancer radiation therapy and PTT.
Data profiling is the computer science discipline of analyzing a given dataset for its metadata. The types of metadata range from basic statistics, such as tuple counts, column aggregations, and value distributions, to much more complex structures, in particular inclusion dependencies (INDs), unique column combinations (UCCs), and functional dependencies (FDs). If present, these statistics and structures serve to efficiently store, query, change, and understand the data. Most datasets, however, do not provide their metadata explicitly so that data scientists need to profile them.
While basic statistics are relatively easy to calculate, more complex structures present difficult, mostly NP-complete discovery tasks; even with good domain knowledge, it is hardly possible to detect them manually. Therefore, various profiling algorithms have been developed to automate the discovery. None of them, however, can process datasets of typical real-world size, because their resource consumptions and/or execution times exceed effective limits.
In this thesis, we propose novel profiling algorithms that automatically discover the three most popular types of complex metadata, namely INDs, UCCs, and FDs, which all describe different kinds of key dependencies. The task is to extract all valid occurrences from a given relational instance. The three algorithms build upon known techniques from related work and complement them with algorithmic paradigms, such as divide & conquer, hybrid search, progressivity, memory sensitivity, parallelization, and additional pruning to greatly improve upon current limitations. Our experiments show that the proposed algorithms are orders of magnitude faster than related work. They are, in particular, now able to process datasets of real-world, i.e., multiple gigabytes size with reasonable memory and time consumption.
Due to the importance of data profiling in practice, industry has built various profiling tools to support data scientists in their quest for metadata. These tools provide good support for basic statistics and they are also able to validate individual dependencies, but they lack real discovery features even though some fundamental discovery techniques are known for more than 15 years. To close this gap, we developed Metanome, an extensible profiling platform that incorporates not only our own algorithms but also many further algorithms from other researchers. With Metanome, we make our research accessible to all data scientists and IT-professionals that are tasked with data profiling. Besides the actual metadata discovery, the platform also offers support for the ranking and visualization of metadata result sets.
Being able to discover the entire set of syntactically valid metadata naturally introduces the subsequent task of extracting only the semantically meaningful parts. This is challenge, because the complete metadata results are surprisingly large (sometimes larger than the datasets itself) and judging their use case dependent semantic relevance is difficult. To show that the completeness of these metadata sets is extremely valuable for their usage, we finally exemplify the efficient processing and effective assessment of functional dependencies for the use case of schema normalization.