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Numerous reports of relatively rapid climate changes over the past century make a clear case of the impact of aerosols and clouds, identified as sources of largest uncertainty in climate projections. Earth’s radiation balance is altered by aerosols depending on their size, morphology and chemical composition. Competing effects in the atmosphere can be further studied by investigating the evolution of aerosol microphysical properties, which are the focus of the present work.
The aerosol size distribution, the refractive index, and the single scattering albedo are commonly used such properties linked to aerosol type, and radiative forcing. Highly advanced lidars (light detection and ranging) have reduced aerosol monitoring and optical profiling into a routine process. Lidar data have been widely used to retrieve the size distribution through the inversion of the so-called Lorenz-Mie model (LMM). This model offers a reasonable treatment for spherically approximated particles, it no longer provides, though, a viable description for other naturally occurring arbitrarily shaped particles, such as dust particles. On the other hand, non-spherical geometries as simple as spheroids reproduce certain optical properties with enhanced accuracy. Motivated by this, we adapt the LMM to accommodate the spheroid-particle approximation introducing the notion of a two-dimensional (2D) shape-size distribution.
Inverting only a few optical data points to retrieve the shape-size distribution is classified as a non-linear ill-posed problem. A brief mathematical analysis is presented which reveals the inherent tendency towards highly oscillatory solutions, explores the available options for a generalized solution through regularization methods and quantifies the ill-posedness. The latter will improve our understanding on the main cause fomenting instability in the produced solution spaces. The new approach facilitates the exploitation of additional lidar data points from depolarization measurements, associated with particle non-sphericity. However, the generalization of LMM vastly increases the complexity of the problem. The underlying theory for the calculation of the involved optical cross sections (T-matrix theory) is computationally so costly, that would limit a retrieval analysis to an unpractical point. Moreover the discretization of the model equation by a 2D collocation method, proposed in this work, involves double integrations which are further time consuming. We overcome these difficulties by using precalculated databases and a sophisticated retrieval software (SphInX: Spheroidal Inversion eXperiments) especially developed for our purposes, capable of performing multiple-dataset inversions and producing a wide range of microphysical retrieval outputs.
Hybrid regularization in conjunction with minimization processes is used as a basis for our algorithms. Synthetic data retrievals are performed simulating various atmospheric scenarios in order to test the efficiency of different regularization methods. The gap in contemporary literature in providing full sets of uncertainties in a wide variety of numerical instances is of major concern here. For this, the most appropriate methods are identified through a thorough analysis on an overall-behavior basis regarding accuracy and stability. The general trend of the initial size distributions is captured in our numerical experiments and the reconstruction quality depends on data error level. Moreover, the need for more or less depolarization points is explored for the first time from the point of view of the microphysical retrieval. Finally, our approach is tested in various measurement cases giving further insight for future algorithm improvements.
Möglichkeiten der Mittelstandsförderung durch Vergaberechtsgestaltung und Vergaberechtspraxis
(2016)
Die Förderungswürdigkeit und die Förderungsfähigkeit mittelständischer Unternehmen ist ein gesamteuropäisches, wirtschaftspolitisches Anliegen. Hiervon zeugen zum einen zahlreiche Regelungen im Primär-, Sekundär-, Verfassungs- und einfachgesetzlichem Recht, zum anderen auch die Bedeutung der mittelständischen Unternehmen im wirtschaftlichen, gesellschaftlichen und sozialen Gefüge. So herrscht innerhalb der Europäischen Union nicht nur der Slogan „Vorfahrt für KMU“, sondern auch die im Frühjahr 2014 verabschiedeten Vergaberichtlinien legten ein besonderes Augenmerk auf die Förderung des Zugangs der KMU zum öffentlichen Beschaffungsmarkt. Denn gemessen am Steuerungs- und Lenkungspotenzial der Auftragsvergabe, deren Einfluss auf die Innovationstätigkeit der Wirtschaft sowie deren Auswirkungen auf die Wirtschafts- und Wettbewerbstätigkeit auf der einen Seite und dem gesamtwirtschaftlichen Stellenwert der mittelständischen Unternehmen auf der anderen Seite, sind mittelständische Unternehmen trotz zahlreicher europäischer und nationaler Initiativen im Vergabeverfahren unterrepräsentiert. Neben der undurchsichtigen Regelungsstruktur des deutschen Vergaberechts, unterliegen die mittelständischen Unternehmen vom Beginn bis zum Ende des Vergabeverfahrens besonderen Schwierigkeiten. Dieser Ausgangsbefund wurde zum Anlass genommen, um die Möglichkeiten der Mittelstandsförderung durch Vergaberechtsgestaltung und Vergaberechtspraxis erneut auf den Prüfstand zu stellen.
Infants' lexical processing is modulated by featural manipulations made to words, suggesting that early lexical representations are sufficiently specified to establish a match with the corresponding label. However, the precise degree of detail in early words requires further investigation due to equivocal findings. We studied this question by assessing children’s sensitivity to the degree of featural manipulation (Chapters 2 and 3), and sensitivity to the featural makeup of homorganic and heterorganic consonant clusters (Chapter 4). Gradient sensitivity on the one hand and sensitivity to homorganicity on the other hand would suggest that lexical processing makes use of sub-phonemic information, which in turn would indicate that early words contain sub-phonemic detail. The studies presented in this thesis assess children’s sensitivity to sub-phonemic detail using minimally demanding online paradigms suitable for infants: single-picture pupillometry and intermodal preferential looking. Such paradigms have the potential to uncover lexical knowledge that may be masked otherwise due to cognitive limitations. The study reported in Chapter 2 obtained a differential response in pupil dilation to the degree of featural manipulation, a result consistent with gradient sensitivity. The study reported in Chapter 3 obtained a differential response in proportion of looking time and pupil dilation to the degree of featural manipulation, a result again consistent with gradient sensitivity. The study reported in Chapter 4 obtained a differential response to the manipulation of homorganic and heterorganic consonant clusters, a result consistent with sensitivity to homorganicity. These results suggest that infants' lexical representations are not only specific, but also detailed to the extent that they contain sub-phonemic information.
Das Widerspenstige bändigen
(2016)
Dem Handeln von Lehrkräften wird in der schulischen Praxis wie in der wissenschaftlichen Literatur ein wesentlicher Einfluss auf die Qualität von schulischem Unterricht zugesprochen. Auch wenn umfangreiche normative Vorstellungen über ein gutes Lehr-Handeln bestehen, so gibt es wenig Erkenntnis darüber, welche Gründe Lehrkräfte für ihr pädagogisches Handeln haben. Das Handeln von Lehrkräften kann nur dann adäquat erfasst werden, wenn Bildung einerseits als Weitergabe von Kultur an die nachfolgende Generation und andererseits als eine vom sich bildenden Subjekt ausgehende Selbst- und Weltverständigung verstanden wird. Damit einhergehende Anforderungen an die Lehrkraft stehen notwendigerweise in Widerspruch zueinander; dies gilt besonders für eine Gesellschaft mit großer kultureller und sozialer Heterogenität. Bei der Suche nach Zusammenhängen zwischen Persönlichkeit, pädagogischem Wissen oder Kompetenzen und einem unterrichtlichen Handeln wird häufig von einer Bedingtheit dieses Handelns ausgegangen und dieses auf kognitive Aspekte und an externen Normen orientierte Merkmale verkürzt. Ertragreicher für eine Antwort auf die Frage nach den Begründungen sind wissenschaftliche Arbeiten, die Professionalität als eine Bezugnahme auf einen besonderen strukturellen Rahmen beschreiben, der durch Widersprüche geprägt ist und Entscheidungen zu den Spannungsfeldern pädagogischer Verhältnisse erfordert. Die subjektwissenschaftliche Lerntheorie bietet eine Basis für ein Verständnis eines Lernens in institutionellen Kontexten ausgehend von den Lerninteressen der Schülerinnen und Schüler. Lehren kann darauf bezugnehmend als Unterstützung von Selbst- und Weltverständigungsprozessen durch Wertschätzung, Verstehen und Angebote alternativer Bedeutungshorizonte verstanden werden. Das Handeln von Lehrkräften ist als sinngebende Bezugnahme auf daraus resultierende sowie institutionelle Anforderungen mittels gesellschaftlicher Bedeutungsstrukturen verstehbar. Das handelnde Subjekt erschließt sich selbst und die Welt mit Hilfe von Bedeutungen. Diese können verstanden werden als der Besonderheit der Biographie, der gesellschaftlichen Position sowie der Lebenslage geschuldete Reinterpretationen gesellschaftlicher Bedeutungsstrukturen. Im empirischen Verfahren können mittels eines Übergangs von sequentiellen zu komparativen Analysen Positionierungen als thematisch spezifische und über die konkrete Handlungssituation hinausreichende Bedeutungs-Begründungs-Zusammenhänge rekonstruiert werden. Daraus werden situationsunabhängige Strukturmomente des Gegenstands Lehren an beruflichen Schulen aber auch komplexe, situationsbezogene subjektive Bedeutungs-Begründungs-Muster abgeleitet. Als wesentliche strukturelle Merkmale lassen sich die Schlüsselkategorien ‚Deutungsmacht‘ und ‚instrumentelle pädagogische Beziehung‘ aus dem empirischen Material unter Zuhilfenahme weiterer theoretischer Folien entwickeln. Da Deutungsmacht auf Akzeptanz angewiesen ist und in instrumentellen Beziehungen eine kooperative Bezugnahme auf den Lehr-Lern-Gegenstand allenfalls punktuell erfolgt, können damit asymmetrische metastabile Arrangements zwischen einer Lehrkraft und Schülerinnen und Schülern verstanden werden. Als empirische Ausprägungen weist Deutungsmacht die Varianten ‚absoluter Anspruch‘, ‚Akzeptanz der Fragilität‘ und ‚Akzeptanz der Legitimität eines Infragestellens‘ auf. Bei der zweiten Schlüsselkategorie treten die Varianten ‚strukturelle Prägung‘, ‚unspezifischer allgemein-menschlicher Charakter‘ und ‚Außenprägung‘ der instrumentellen pädagogischen Beziehung auf. Die Bedeutungs-Begründungs-Musters weisen teilweise Inkonsistenzen und Übergänge in den Positionierungen bezogen auf die dargestellten Varianten auf. Nur bei einem Teil der Muster sind Bemühungen um Wertschätzung und Verstehen der Schülerinnen und Schüler plausibel ableitbar, gleiches gilt in Hinblick auf eine Offenheit für eine Revision der Muster. Die Muster, wie etwa ‚Durchsetzend-ertragendes Nachsteuern‘, ‚Direktiv-personalisierendes Praktizieren‘ oder ‚Regulierend-flexibles Managen‘ sind zu verstehen als Bewältigungsmodi der kontingenten pädagogischen (Konflikt-)Situationen, auf die sich die Fallschilderungen beziehen. Die jeweilige Lehrkraft hat dieses Muster in dem beschriebenen Fall genutzt, was allerdings keine Aussage darüber zulässt, auf welche Muster die Lehrkraft in anderen Fällen zugreifen würde. Die Ergebnisse der vorliegenden Arbeit eignen sich als eine heuristische bzw. theoretische Folie, die Lehrkräfte beim Erschließen ihres eigenen pädagogischen Handelns - etwa in einer als Fallberatung konzipierten Fortbildung - unterstützen kann. Möglich sind Anschlüsse an andere theoretische Ansätze zum Handeln von Lehrkräften aber auch deren veränderte Einordnung. Erweitert werden die Optionen, dieses Handeln über wissenschaftliche Zugänge zu erfassen.
Eye movements serve as a window into ongoing visual-cognitive processes and can thus be used to investigate how people perceive real-world scenes. A key issue for understanding eye-movement control during scene viewing is the roles of central and peripheral vision, which process information differently and are therefore specialized for different tasks (object identification and peripheral target selection respectively). Yet, rather little is known about the contributions of central and peripheral processing to gaze control and how they are coordinated within a fixation during scene viewing. Additionally, the factors determining fixation durations have long been neglected, as scene perception research has mainly been focused on the factors determining fixation locations. The present thesis aimed at increasing the knowledge on how central and peripheral vision contribute to spatial and, in particular, to temporal aspects of eye-movement control during scene viewing. In a series of five experiments, we varied processing difficulty in the central or the peripheral visual field by attenuating selective parts of the spatial-frequency spectrum within these regions. Furthermore, we developed a computational model on how foveal and peripheral processing might be coordinated for the control of fixation duration. The thesis provides three main findings. First, the experiments indicate that increasing processing demands in central or peripheral vision do not necessarily prolong fixation durations; instead, stimulus-independent timing is adapted when processing becomes too difficult. Second, peripheral vision seems to play a prominent role in the control of fixation durations, a notion also implemented in the computational model. The model assumes that foveal and peripheral processing proceed largely in parallel and independently during fixation, but can interact to modulate fixation duration. Thus, we propose that the variation in fixation durations can in part be accounted for by the interaction between central and peripheral processing. Third, the experiments indicate that saccadic behavior largely adapts to processing demands, with a bias of avoiding spatial-frequency filtered scene regions as saccade targets. We demonstrate that the observed saccade amplitude patterns reflect corresponding modulations of visual attention. The present work highlights the individual contributions and the interplay of central and peripheral vision for gaze control during scene viewing, particularly for the control of fixation duration. Our results entail new implications for computational models and for experimental research on scene perception.
Water scarcity, adaption on climate change, and risk assessment of droughts and floods are critical topics for science and society these days. Monitoring and modeling of the hydrological cycle are a prerequisite to understand and predict the consequences for weather and agriculture. As soil water storage plays a key role for partitioning of water fluxes between the atmosphere, biosphere, and lithosphere, measurement techniques are required to estimate soil moisture states from small to large scales.
The method of cosmic-ray neutron sensing (CRNS) promises to close the gap between point-scale and remote-sensing observations, as its footprint was reported to be 30 ha. However, the methodology is rather young and requires highly interdisciplinary research to understand and interpret the response of neutrons to soil moisture. In this work, the signal of nine detectors has been systematically compared, and correction approaches have been revised to account for meteorological and geomagnetic variations. Neutron transport simulations have been consulted to precisely characterize the sensitive footprint area, which turned out to be 6--18 ha, highly local, and temporally dynamic. These results have been experimentally confirmed by the significant influence of water bodies and dry roads. Furthermore, mobile measurements on agricultural fields and across different land use types were able to accurately capture the various soil moisture states. It has been further demonstrated that the corresponding spatial and temporal neutron data can be beneficial for mesoscale hydrological modeling. Finally, first tests with a gyrocopter have proven the concept of airborne neutron sensing, where increased footprints are able to overcome local effects.
This dissertation not only bridges the gap between scales of soil moisture measurements. It also establishes a close connection between the two worlds of observers and modelers, and further aims to combine the disciplines of particle physics, geophysics, and soil hydrology to thoroughly explore the potential and limits of the CRNS method.
This two-wave longitudinal study examined how developmental changes in students’ mastery goal orientation, academic effort, and intrinsic motivation were predicted by student-perceived support of motivational support (support for autonomy, competence, and relatedness) in secondary classrooms. The study extends previous knowledge that showed that support for motivational support in class is related to students’ intrinsic motivation as it focused on the developmental changes of a set of different motivational variables and the relations of these changes to student-perceived motivational support in class. Thus, differential classroom effects on students’ motivational development were investigated. A sample of 1088 German students was assessed in the beginning of the school year when students were in grade 8 (Mean age D 13.70, SD D 0.53, 54% girls) and again at the end of the next school year when students were in grade 9. Results of latent change models showed a tendency toward decline in mastery goal orientation and a significant decrease in academic effort from grade 8 to 9. Intrinsic motivation did not decrease significantly across time. Student-perceived support of competence in class predicted the level and change in students’ academic effort. The findings emphasized that it is beneficial to create classroom learning environments that enhance students’ perceptions of competence in class when aiming to enhance students’ academic effort in secondary school classrooms.
Subcultures creating culture
(2016)
The purpose of this work is to apply the methods of textual semiotics to subcultures, in particular to the little known glam subculture. Subcultures have been the main research field of the Birmingham Centre for Contemporary Cultural Studies, known for its interdisciplinary approach, and for its focus on the creative aspects of subculture. Hebdige, in particular, introduced many semiotic elements in his work, as the aberrant decoding after Eco and the cultural creativity via bricolage after Lévi-Strauss. His definition of subculture as symbolic resistance has been criticized by the following post-subcultural researchers for its abstractness and lack of cohesion.
Semiotics eventually have been expelled from the set of tools used in sociology for the analysis of subcultures. Nowadays, the studies on subcultures have a strong ethnographic focus. Due to terminological proliferation and a descriptive approach, it is difficult to compare them on a common basis.
Textual semiotics, through the concept of semiosphere developed by Lotman, allows to go back to the intuitions of Hebdige, organizing the semiotic elements already present in his work into a wider system of interpretation. The semiosphere offers a coherent theoretical horizon as a basis for further analysis, and a new methodological perspective focusing on the cultural. In this thesis for the first time the work of Lotman is applied to the study of a subculture.
Dietary approaches contribute to the prevention and treatment of type 2 diabetes. High protein diets were shown to exert beneficial as well as adverse effects on metabolism. However, it is unclear whether the protein origin plays a role in these effects. The LeguAN study investigated in detail the effects of two high protein diets, either from plant or animal origin, in type 2 diabetic patients. Both diets contained 30 EN% protein, 40 EN% carbohydrates, and 30 EN% fat. Fiber content, glycemic index, and composition of dietary fats were similar in both diets. In comparison to previous dietary habits, the fat content was exchanged for protein, while the carbohydrate intake was not modified. Overall, both high protein diets led to improvements of glycemic control, insulin sensitivity, liver fat, and cardiovascular risk markers without remarkable differences between the protein types.
Fasting glucose together with indices of insulin resistance were ameliorated by both interventions to varying extents but without significant differences between protein types. The decline of HbA1c was more pronounced in the plant protein group, whereby the improvement of insulin sensitivity in the animal protein group. The high protein intake had only slight influence on postprandial metabolism seen for free fatty acids and indices of insulin secretion, sensitivity and degradation. Except for GIP release, ingestion of animal and plant meals did not provoke differential metabolic and hormonal responses despite diverse circulating amino acid levels.
The animal protein diets led to a selective increase of fat-free mass and decrease of total fat mass, which was not significantly different from the plant protein diet. Moreover, the high protein diets potently decreased liver fat content by 42% on average which was linked to significantly diminished lipogenesis, free fatty acids flux and lipolysis in adipose tissue. Moderate decline of circulating liver enzymes was induced by both interventions. The liver fat reduction was associated with improved glucose homeostasis and insulin sensitivity which underlines the protective effect of the diets.
Blood lipid profile improved in all subjects and was probably related to the lower fat intake. Reductions in uric acid and markers of inflammation further argued for metabolic benefits of both high protein diets. Systolic and diastolic blood pressure declined only in the PP group pointing a possible role of arginine.
Kidney function was not altered by high protein consumption over 6 weeks. The rapid decrease of serum creatinine in the PP group was noteworthy and should be further investigated. Protein type did not seem to play a role but long-term studies are warranted to fully elucidate safety of high protein regimen.
Varying the source of dietary proteins did not affect the mTOR pathway in adipose tissue and blood cells under neither acute nor chronic settings. Enhancement of whole-body insulin sensitivity suggested also no alteration of mTOR and no impairment of insulin sensitivity in skeletal muscle.
A remarkable outcome was the extensive reduction of FGF21, critical regulator of metabolic processes, by approximately 50% independently of protein type. Whether hepatic ER-stress, ammonia flux or rather macronutrient preferences is behind this paradoxical finding remains to be investigated in detail.
Unlike initial expectations and previous reports plant protein based diet had no clear advantage over animal proteins. The pronounced beneficial effect of animal protein on insulin homeostasis despite high BCAA and methionine intake was certainly unexpected assuming more complex metabolic adaptations occurring upon prolonged consumption. In addition, the reduced fat intake may have also contributed to the overall improvements in both groups.
Taking into account the above observed study results, a short-term diet containing 30 EN% protein (either from plant or animal origin), 40 EN% carbohydrates, and 30 EN% fat with lower SFA amount leads to metabolic improvements in diabetic patients, regardless of protein source.
The present work is a case study contributing to the major planning project “Suedlink”. It is structured as follows: first, in a theoretical part, mandatory theories of social acceptance (Wüstenhagen et al., 2007), steps of participation (Münnich, 2014), and the governance theory (Benz and Dose, 2011) are elaborated. Secondly, the relevant methods are discussed. Thirdly, in a qualitative analytical part, the information that were gathered from the expert interviews are analyzed with the use of the aforementioned theories. In the fourth place, an empirical quantitative analysis of data regarding the public acceptance towards Suedlink is presented.
In this case study, with the use of qualitative and quantitative methods, two questions are answered: first, which governance aspects were relevant for the priority use of underground cables for the construction of high voltage direct current transmission lines? For this question, intensive document analysis and different expert interviews were conducted. Secondly, the central question of the present work addresses the question whether local or/and individual factors affect the public acceptance towards SüdLink. Here, in particular, it is interesting to analyze if the priority use of underground cables affected the people’s acceptance towards SuedLink. In order to respond to both questions, an online survey was conducted among citizen initiatives, district administrators, and individuals in social media during March till July 2016. Thereafter, the data was analyzed with the use of descriptive quantitative methods. The data shows, that underground cables not necessarily increase public acceptance (see also Menges and Beyer, 2013). On the contrary, individual and local criteria were relevant for the survey respondents. For example criteria such as the quality of participation, distance between home and transmission lines, and the additional financial burden (taxes, higher prices for electricity) were important for the evaluation. In addition, survey respondents who participated in citizen initiatives were more critical against the priority use of underground cables and SuedLink in general. Likewise, residential homeowners rejected every form of transmission lines.
Durch die Zunahme metabolischer Stoffwechselstörungen und Erkrankungen in der Weltbevölkerung wird in der Medizin und den Lebenswissenschaften vermehrt nach Präventionsstrategien und Ansatzpunkten gesucht, die die Gesundheit fördern, Erkrankungen verhindern helfen und damit auch die Gesamtlast auf die Gesundheitssysteme erleichtern. Ein Ansatzpunkt wird dabei in der Ernährung gesehen, da insbesondere der Konsum von gesättigten Fetten die Gesundheit nachträglich zu beeinflussen scheint. Dabei wird übersehen, dass in vielen Studien Hochfettdiäten nicht ausreichend von den Einflüssen einer zum Bedarf hyperkalorischen Energiezufuhr getrennt werden, sodass die Datenlage zu dem Einfluss von (gesättigten) Fetten auf den Metabolismus bei gleichbleibender Energieaufnahme noch immer unzureichend ist.
In der NUtriGenomic Analysis in Twins-Studie wurden 46 Zwillingspaare (34 monozygot, 12 dizygot) über einen Zeitraum von sechs Wochen mittels einer kohlenhydratreichen, fettarmen Diät nach Richtlinien der Deutschen Gesellschaft für Ernährung für ihr Ernährungsverhalten standardisiert, ehe sie zu einer kohlenhydratarmen, fettreichen Diät, die insbesondere gesättigte Fette enthielt, für weitere sechs Wochen wechselten. Beide Diäten waren dem individuellen Energiebedarf der Probanden angepasst, um so sowohl akut nach einerWoche als auch längerfristig nach sechs Wochen Änderungen des Metabolismus beobachten zu können, die sich in der vermehrten Aufnahme von (gesättigten) Fetten begründeten.
Die über die detaillierte Charakterisierung der Probanden an den klinischen Untersuchungstagen generierten Datensätze wurden mit statistischen und mathematischen Methoden (z.B. lineare gemischte Modellierung) analysiert, die der Größe der Datensätze und damit ihrem Informationsvolumen angepasst waren.
Es konnte gezeigt werden, dass die metabolisch gesunden und relativ jungen Probanden, die eine gute Compliance zeigten, im Hinblick auf ihren Glukosestoffwechsel adaptieren konnten, indem die Akutantwort nach einer Woche im Nüchterninsulin und dem Index für Insulinresistenz in den weiteren fünf Wochen ausgeglichen wurde.
Der Lipidstoffwechsel in Form der klassischen Marker wie Gesamtcholesterin, LDL und HDL war dagegen stärker beeinflusst und auch nach insgesamt sechs Wochen deutlich erhöht.
Letzteres unterstützt die Beobachtung im Transkriptom des weißen, subkutanen Fettgewebes, bei der eine Aktivierung der über die Toll-like receptors und das Inflammasom vermittelten subklinischen Inflammation beobachtet werden konnte.
Die auftretenden Veränderungen in Konzentration und Komposition des Plasmalipidoms zeigte ebenfalls nur eine teilweise und auf bestimmte Spezies begrenzte Gegenregulation.
Diesbezüglich kann also geschlussfolgert werden, dass auch die isokalorische Aufnahme von (gesättigten) Fetten zu Veränderungen im Metabolismus führt, wobei die Auswirkungen in weiteren (Langzeit-)Studien und Experimenten noch genauer untersucht werden müssen. Insbesondere wäre dabei ein längerer Zeitraum unter isokalorischen Bedingungen von Interesse und die Untersuchung von Probanden mit metabolischer Vorbelastung (z.B. Insulinresistenz).
Darüber hinaus konnte in NUGAT aber ebenfalls gezeigt werden, dass die Nutrigenetik und Nutrigenomik zwei nicht zu vernachlässigende Faktoren darstellen. So zeigten unter anderem die Konzentrationen einiger Lipidspezies eine starke Erblichkeit und Abhängigkeit der Diät.
Zudem legen die Ergebnisse nahe, dass laufende wie geplante Präventionsstrategien und medizinische Behandlungen deutlich stärker den Patienten als Individuum mit einbeziehen müssen, da die Datenanalyse interindividuelle Unterschiede identifizierte und Hinweise lieferte, dass einige Probanden die nachteiligen, metabolischen Auswirkungen einer Hochfettdiät besser ausgleichen konnten als andere.
Der Fall der Rachel Dolezal
(2016)
Die Amerikanerin Rachel Dolezal war bis ins Jahr 2015 als Afroamerikanerin bekannt. Als Aktivistin der National Association for the Advancement of Colored People setzte sie sich für die Rechte der afroamerikanischen Bevölkerung ein, lebte in einem schwarzen Umfeld und lehrte an einer Universität Afroamerikanische Studien. „I identify as black“ antwortete sie auf die Frage eines amerikanischen Fernsehmoderators, ob sie Afroamerikanerin sei. Ihre Kollegen und ihr näheres Umfeld identifizierten sie ebenfalls als solche. Erst, als regionale Journalisten auf sie aufmerksam wurden und ihre Eltern sich zu Wort meldeten, wurde deutlich, dass Dolezal eigentlich eine weiße Frau ist. Dolezals Eltern bestätigten dies, indem sie Kindheitsfotos einer hellhäutigen, blonden Rachel veröffentlichten. Dolezals Verhalten entfachte daraufhin eine rege mediale Diskussion über ihre Person im Kontext von Ethnizität und »Rasse«.
Die Verfasserin greift Dolezals Fall exemplarisch auf, um der Frage nachzugehen, ob ein Doing Race nach Belieben möglich ist. Darf sich Dolezal als schwarz identifizieren, obwohl sie keine afrikanischen Vorfahren hat? Welche gesellschaftliche Wissensvorräte schränken diese Wahl ein und welche Konsequenzen ergeben sich daraus? Anhand einer Diskursanalyse amerikanischer Zeitungsartikel geht die Verfasserin diesen Fragen nach. Hierbei werden »Rasse« und Ethnizität als soziale Konstruktionen, basierend auf dem Konzept von Stephen Cornell und Douglas Hartmann, betrachtet.
The optical properties of semiconductor nanocrystals (SC NCs) are largely controlled by their size and surface chemistry, i.e., the chemical composition and thickness of inorganic passivation shells and the chemical nature and number of surface ligands as well as the strength of their bonds to surface atoms. The latter is particularly important for CdTe NCs, which – together with alloyed CdxHg1−xTe – are the only SC NCs that can be prepared in water in high quality without the need for an additional inorganic passivation shell. Aiming at a better understanding of the role of stabilizing ligands for the control of the application-relevant fluorescence features of SC NCs, we assessed the influence of two of the most commonly used monodentate thiol ligands, thioglycolic acid (TGA) and mercaptopropionic acid (MPA), on the colloidal stability, photoluminescence (PL) quantum yield (QY), and PL decay behavior of a set of CdTe NC colloids. As an indirect measure for the strength of the coordinative bond of the ligands to SC NC surface atoms, the influence of the pH (pD) and the concentration on the PL properties of these colloids was examined in water and D2O and compared to the results from previous dilution studies with a set of thiol-capped Cd1−xHgxTe SC NCs in D2O. As a prerequisite for these studies, the number of surface ligands was determined photometrically at different steps of purification after SC NC synthesis with Ellman's test. Our results demonstrate ligand control of the pH-dependent PL of these SC NCs, with MPA-stabilized CdTe NCs being less prone to luminescence quenching than TGA-capped ones. For both types of CdTe colloids, ligand desorption is more pronounced in H2O compared to D2O, underlining also the role of hydrogen bonding and solvent molecules.
The collision of bathymetric anomalies, such as oceanic spreading centers, at convergent plate margins can profoundly affect subduction dynamics, magmatism, and the structural and geomorphic evolution of the overriding plate. The Southern Patagonian Andes of South America are a prime example for sustained oceanic ridge collision and the successive formation and widening of an extensive asthenospheric slab window since the Middle Miocene. Several of the predicted upper-plate geologic manifestations of such deep-seated geodynamic processes have been studied in this region, but many topics remain highly debated. One of the main controversial topics is the interpretation of the regional low-temperature thermochronology exhumational record and its relationship with tectonic and/or climate-driven processes, ultimately manifested and recorded in the landscape evolution of the Patagonian Andes. The prominent along-strike variance in the topographic characteristics of the Andes, combined with coupled trends in low-temperature thermochronometer cooling ages have been interpreted in very contrasting ways, considering either purely climatic (i.e. glacial erosion) or geodynamic (slab-window related) controlling factors.
This thesis focuses on two main aspects of these controversial topics. First, based on field observations and bedrock low-temperature thermochronology data, the thesis addresses an existing research gap with respect to the neotectonic activity of the upper plate in response to ridge collision - a mechanism that has been shown to affect the upper plate topography and exhumational patterns in similar tectonic settings. Secondly, the qualitative interpretation of my new and existing thermochronological data from this region is extended by inverse thermal modelling to define thermal histories recorded in the data and evaluate the relative importance of surface vs. geodynamic factors and their possible relationship with the regional cooling record.
My research is centered on the Northern Patagonian Icefield (NPI) region of the Southern Patagonian Andes. This site is located inboard of the present-day location of the Chile Triple Junction - the juncture between the colliding Chile Rise spreading center and the Nazca and Antarctic Plates along the South American convergent margin. As such this study area represents the region of most recent oceanic-ridge collision and associated slab window formation. Importantly, this location also coincides with the abrupt rise in summit elevations and relief characteristics in the Southern Patagonian Andes. Field observations, based on geological, structural and geomorphic mapping, are combined with bedrock apatite (U-Th)/He and apatite fission track (AHe and AFT) cooling ages sampled along elevation transects across the orogen. This new data reveals the existence of hitherto unrecognized neotectonic deformation along the flanks of the range capped by the NPI.
This deformation is associated with the closely spaced oblique collision of successive oceanic-ridge segments in this region over the past 6 Ma. I interpret that this has caused a crustal-scale partitioning of deformation and the decoupling, margin-parallel migration, and localized uplift of a large crustal sliver (the NPI block) along the subduction margin. The location of this uplift coincides with a major increase of summit elevations and relief at the northern edge of the NPI massif. This mechanism is compatible with possible extensional processes along the topographically subdued trailing edge of the NPI block as documented by very recent and possibly still active normal faulting. Taken together, these findings suggest a major structural control on short-wavelength variations in topography in the Southern Patagonian Andes - the region affected by ridge collision and slab window formation.
The second research topic addressed here focuses on using my new and existing bedrock low-temperature cooling ages in forward and inverse thermal modeling. The data was implemented in the HeFTy and QTQt modeling platforms to constrain the late Cenozoic thermal history of the Southern Patagonian Andes in the region of the most recent upper-plate sectors of ridge collision. The data set combines AHe and AFT data from three elevation transects in the region of the Northern Patagonian Icefield. Previous similar studies claimed far-reaching thermal effects of the approaching ridge collision and slab window to affect patterns of Late Miocene reheating in the modelled thermal histories. In contrast, my results show that the currently available data can be explained with a simpler thermal history than previously proposed. Accordingly, a reheating event is not needed to reproduce the observations. Instead, the analyzed ensemble of modelled thermal histories defines a Late Miocene protracted cooling and Pliocene-to-recent stepwise exhumation. These findings agree with the geological record of this region. Specifically, this record indicates an Early Miocene phase of active mountain building associated with surface uplift and an active fold-and-thrust belt, followed by a period of stagnating deformation, peneplanation, and lack of synorogenic deposition in the Patagonian foreland. The subsequent period of stepwise exhumation likely resulted from a combination of pulsed glacial erosion and coeval neotectonic activity. The differences between the present and previously published interpretation of the cooling record can be reconciled with important inconsistencies of previously used model setup. These include mainly the insufficient convergence of the models and improper assumptions regarding the geothermal conditions in the region. This analysis puts a methodological emphasis on the prime importance of the model setup and the need for its thorough examination to evaluate the robustness of the final outcome.
In this paper we report an experimental and computational study of liquid acetonitrile (H3C–C[triple bond, length as m-dash]N) by resonant inelastic X-ray scattering (RIXS) at the N K-edge. The experimental spectra exhibit clear signatures of the electronic structure of the valence states at the N site and incident-beam-polarization dependence is observed as well. Moreover, we find fine structure in the quasielastic line that is assigned to finite scattering duration and nuclear relaxation. We present a simple and light-to-evaluate model for the RIXS maps and analyze the experimental data using this model combined with ab initio molecular dynamics simulations. In addition to polarization-dependence and scattering-duration effects, we pinpoint the effects of different types of chemical bonding to the RIXS spectrum and conclude that the H2C–C[double bond, length as m-dash]NH isomer, suggested in the literature, does not exist in detectable quantities. We study solution effects on the scattering spectra with simulations in liquid and in vacuum. The presented model for RIXS proved to be light enough to allow phase-space-sampling and still accurate enough for identification of transition lines in physical chemistry research by RIXS.
The excitation of localized surface plasmons in noble metal nanoparticles (NPs) results in different nanoscale effects such as electric field enhancement, the generation of hot electrons and a temperature increase close to the NP surface. These effects are typically exploited in diverse fields such as surface-enhanced Raman scattering (SERS), NP catalysis and photothermal therapy (PTT). Halogenated nucleobases are applied as radiosensitizers in conventional radiation cancer therapy due to their high reactivity towards secondary electrons. Here, we use SERS to study the transformation of 8-bromoadenine (8BrA) into adenine on the surface of Au and AgNPs upon irradiation with a low-power continuous wave laser at 532, 633 and 785 nm, respectively. The dissociation of 8BrA is ascribed to a hot-electron transfer reaction and the underlying kinetics are carefully explored. The reaction proceeds within seconds or even milliseconds. Similar dissociation reactions might also occur with other electrophilic molecules, which must be considered in the interpretation of respective SERS spectra. Furthermore, we suggest that hot-electron transfer induced dissociation of radiosensitizers such as 8BrA can be applied in the future in PTT to enhance the damage of tumor tissue upon irradiation.
Macrocycles based on L-cystine were synthesized by ring-closing metathesis (RCM) and subsequently polymerized by entropy-driven ring-opening metathesis polymerization (ED-ROMP). Monomer conversion reached ∼80% in equilibrium and the produced poly(ester-amine-disulfide-alkene)s exhibited apparent molar masses (Mappw) of up to 80 kDa and dispersities (Đ) of ∼2. The polymers can be further functionalized with acid anhydrides and degraded by reductive cleavage of the main-chain disulfide.
Savannas cover a broad geographical range across continents and are a biome best described by a mix of herbaceous and woody plants. The former create a more or less continuous layer while the latter should be sparse enough to leave an open canopy. What has long intrigued ecologists is how these two competing plant life forms of vegetation coexist.
Initially attributed to resource competition, coexistence was considered the stable outcome of a root niche differentiation between trees and grasses. The importance of environmental factors became evident later, when data from moister environments demonstrated that tree cover was often lower than what the rainfall conditions would allow for. Our current understanding relies on the interaction of competition and disturbances in space and time. Hence, the influence of grazing and fire and the corresponding feedbacks they generate have been keenly investigated. Grazing removes grass cover, initiating a self-reinforcing process propagating tree cover expansion. This is known as the encroachment phenomenon. Fire, on the other hand, imposes a bottleneck on the tree population by halting the recruitment of young trees into adulthood. Since grasses fuel fires, a feedback linking grazing, grass cover, fire, and tree cover is created. In African savannas, which are the focus of this dissertation, these feedbacks play a major role in the dynamics.
The importance of these feedbacks came into sharp focus when the notion of alternative states began to be applied to savannas. Alternative states in ecology arise when different states of an ecosystem can occur under the same conditions. According to this an open savanna and a tree-dominated savanna can be classified as alternative states, since they can both occur under the same climatic conditions. The aforementioned feedbacks are critical in the creation of alternative states. The grass-fire feedback can preserve an open canopy as long as fire intensity and frequency remain above a certain threshold. Conversely, crossing a grazing threshold can force an open savanna to shift to a tree-dominated state. Critically, transitions between such alternative states can produce hysteresis, where a return to pre-transition conditions will not suffice to restore the ecosystem to its original state.
In the chapters that follow, I will cover aspects relating to the coexistence mechanisms and the role of feedbacks in tree-grass interactions. Coming back to the coexistence question, due to the overwhelming focus on competition and disturbance another important ecological process was neglected: facilitation. Therefore, in the first study within this dissertation I examine how facilitation can expand the tree-grass coexistence range into drier conditions. For the second study I focus on another aspect of savanna dynamics which remains underrepresented in the literature: the impacts of inter-annual rainfall variability upon savanna trees and the resilience of the savanna state. In the third and final study within this dissertation I approach the well-researched encroachment phenomenon from a new perspective: I search for an early warning indicator of the process to be used as a prevention tool for savanna conservation. In order to perform all this work I developed a mathematical ecohydrological model of Ordinary Differential Equations (ODEs) with three variables: soil moisture content, grass cover and tree cover.
Facilitation: Results showed that the removal of grass cover through grazing was detrimental to trees under arid conditions, contrary to expectation based on resource competition. The reason was that grasses preserved moisture in the soil through infiltration and shading, thus ameliorating the harsh conditions for trees in accordance with the Stress Gradient Hypothesis. The exclusion of grasses from the model further demonstrated this: tree cover was lower in the absence of grasses, indicating that the benefits of grass facilitation outweighed the costs of grass competition for trees. Thus, facilitation expanded the climatic range where savannas persisted into drier conditions.
Rainfall variability: By adjusting the model to current rainfall patterns in East Africa, I simulated conditions of increasing inter-annual rainfall variability for two distinct mean rainfall scenarios: semi-arid and mesic. Alternative states of tree-less grassland and tree-dominated savanna emerged in both cases. Increasing variability reduced semi-arid savanna tree cover to the point that at high variability the savanna state was eliminated, because variability intensified resource competition and strengthened the fire disturbance during high rainfall years. Mesic savannas, on the other hand, became more resilient along the variability gradient: increasing rainfall variability created more opportunities for the rapid growth of trees to overcome the fire disturbance, boosting the chances of savannas persisting and thus increasing mesic savanna resilience.
Preventing encroachment: The breakdown in the grass-fire feedback caused by heavy grazing promoted the expansion of woody cover. This could be irreversible due to the presence of alternative states of encroached and open savanna, which I found along a simulated grazing gradient. When I simulated different short term heavy grazing treatments followed by a reduction to the original grazing conditions, certain cases converged to the encroached state. Utilising woody cover changes only during the heavy grazing treatment, I developed an early warning indicator which identified these cases with a high risk of such hysteresis and successfully distinguished them from those with a low risk. Furthermore, after validating the indicator on encroachment data, I demonstrated that it appeared early enough for encroachment to be prevented through realistic grazing-reduction treatments.
Though this dissertation is rooted in the theory of savanna dynamics, its results can have significant applications in savanna conservation. Facilitation has only recently become a topic of interest within savanna literature. Given the threat of increasing droughts and a general anticipation of drier conditions in parts of Africa, insights stemming from this research may provide clues for preserving arid savannas. The impacts of rainfall variability on savannas have not yet been thoroughly studied, either. Conflicting results appear as a result of the lack of a robust theoretical understanding of plant interactions under variable conditions. . My work and other recent studies argue that such conditions may increase the importance of fast resource acquisition creating a ‘temporal niche’. Woody encroachment has been extensively studied as phenomenon, though not from the perspective of its early identification and prevention. The development of an encroachment forecasting tool, as the one presented in this work, could protect both the savanna biome and societies dependent upon it for (economic) survival. All studies which follow are bound by the attempt to broaden the horizons of savanna-related research in order to deal with extreme conditions and phenomena; be it through the enhancement of the coexistence debate or the study of an imminent external threat or the development of a management-oriented tool for the conservation of savannas.
We present new experimental data of the low-temperature metastable region of liquid water derived from high-density synthetic fluid inclusions (996–916 kg m−3) in quartz. Microthermometric measurements include: (i) prograde (upon heating) and retrograde (upon cooling) liquid–vapour homogenisation. We used single ultrashort laser pulses to stimulate vapour bubble nucleation in initially monophase liquid inclusions. Water densities were calculated based on prograde homogenisation temperatures using the IAPWS-95 formulation. We found retrograde liquid–vapour homogenisation temperatures in excellent agreement with IAPWS-95. (ii) Retrograde ice nucleation. Raman spectroscopy was used to determine the nucleation of ice in the absence of the vapour bubble. Our ice nucleation data in the doubly metastable region are inconsistent with the low-temperature trend of the spinodal predicted by IAPWS-95, as liquid water with a density of 921 kg m−3 remains in a homogeneous state during cooling down to a temperature of −30.5 °C, where it is transformed into ice whose density corresponds to zero pressure. (iii) Ice melting. Ice melting temperatures of up to 6.8 °C were measured in the absence of the vapour bubble, i.e. in the negative pressure region. (iv) Spontaneous retrograde and, for the first time, prograde vapour bubble nucleation. Prograde bubble nucleation occurred upon heating at temperatures above ice melting. The occurrence of prograde and retrograde vapour bubble nucleation in the same inclusions indicates a maximum of the bubble nucleation curve in the ϱ–T plane at around 40 °C. The new experimental data represent valuable benchmarks to evaluate and further improve theoretical models describing the p–V–T properties of metastable water in the low-temperature region.
We present results on ultrafast gas electron diffraction (UGED) experiments with femtosecond resolution using the MeV electron gun at SLAC National Accelerator Laboratory. UGED is a promising method to investigate molecular dynamics in the gas phase because electron pulses can probe the structure with a high spatial resolution. Until recently, however, it was not possible for UGED to reach the relevant timescale for the motion of the nuclei during a molecular reaction. Using MeV electron pulses has allowed us to overcome the main challenges in reaching femtosecond resolution, namely delivering short electron pulses on a gas target, overcoming the effect of velocity mismatch between pump laser pulses and the probe electron pulses, and maintaining a low timing jitter. At electron kinetic energies above 3 MeV, the velocity mismatch between laser and electron pulses becomes negligible. The relativistic electrons are also less susceptible to temporal broadening due to the Coulomb force. One of the challenges of diffraction with relativistic electrons is that the small de Broglie wavelength results in very small diffraction angles. In this paper we describe the new setup and its characterization, including capturing static diffraction patterns of molecules in the gas phase, finding time-zero with sub-picosecond accuracy and first time-resolved diffraction experiments. The new device can achieve a temporal resolution of 100 fs root-mean-square, and sub-angstrom spatial resolution. The collimation of the beam is sufficient to measure the diffraction pattern, and the transverse coherence is on the order of 2 nm. Currently, the temporal resolution is limited both by the pulse duration of the electron pulse on target and by the timing jitter, while the spatial resolution is limited by the average electron beam current and the signal-to-noise ratio of the detection system. We also discuss plans for improving both the temporal resolution and the spatial resolution.
In this contribution, we study using first principles the co-adsorption and catalytic behaviors of CO and O2 on a single gold atom deposited at defective magnesium oxide surfaces. Using cluster models and point charge embedding within a density functional theory framework, we simulate the CO oxidation reaction for Au1 on differently charged oxygen vacancies of MgO(001) to rationalize its experimentally observed lack of catalytic activity. Our results show that: (1) co-adsorption is weakly supported at F0 and F2+ defects but not at F1+ sites, (2) electron redistribution from the F0 vacancy via the Au1 cluster to the adsorbed molecular oxygen weakens the O2 bond, as required for a sustainable catalytic cycle, (3) a metastable carbonate intermediate can form on defects of the F0 type, (4) only a small activation barrier exists for the highly favorable dissociation of CO2 from F0, and (5) the moderate adsorption energy of the gold atom on the F0 defect cannot prevent insertion of molecular oxygen inside the defect. Due to the lack of protection of the color centers, the surface becomes invariably repaired by the surrounding oxygen and the catalytic cycle is irreversibly broken in the first oxidation step.
Information about the strength of donor–acceptor interactions in push–pull alkenes is valuable, as this so-called “push–pull effect” influences their chemical reactivity and dynamic behaviour. In this paper, we discuss the applicability of NMR spectral data and barriers to rotation around the C[double bond, length as m-dash]C double bond to quantify the push–pull effect in biologically important 2-alkylidene-4-oxothiazolidines. While olefinic proton chemical shifts and differences in 13C NMR chemical shifts of the two carbons constituting the C[double bond, length as m-dash]C double bond fail to give the correct trend in the electron withdrawing ability of the substituents attached to the exocyclic carbon of the double bond, barriers to rotation prove to be a reliable quantity in providing information about the extent of donor–acceptor interactions in the push–pull systems studied. In particular all relevant kinetic data, that is the Arrhenius parameters (apparent activation energy Ea and frequency factor A) and activation parameters (ΔS‡, ΔH‡ and ΔG‡), were determined from the data of the experimentally studied configurational isomerization of (E)-9a. These results were compared to previously published related data for other two compounds, (Z)-1b and (2E,5Z)-7, showing that experimentally determined ΔG‡ values are a good indicator of the strength of push–pull character. Theoretical calculations of the rotational barriers of eight selected derivatives excellently correlate with the calculated C[double bond, length as m-dash]C bond lengths and corroborate the applicability of ΔG‡ for estimation of the strength of the push–pull effect in these and related systems.
Coupling of attention and saccades when viewing scenes with central and peripheral degradation
(2016)
Degrading real-world scenes in the central or the peripheral visual field yields a characteristic pattern: Mean saccade amplitudes increase with central and decrease with peripheral degradation. Does this pattern reflect corresponding modulations of selective attention? If so, the observed saccade amplitude pattern should reflect more focused attention in the central region with peripheral degradation and an attentional bias toward the periphery with central degradation. To investigate this hypothesis, we measured the detectability of peripheral (Experiment 1) or central targets (Experiment 2) during scene viewing when low or high spatial frequencies were gaze-contingently filtered in the central or the peripheral visual field. Relative to an unfiltered control condition, peripheral filtering induced a decrease of the detection probability for peripheral but not for central targets (tunnel vision). Central filtering decreased the detectability of central but not of peripheral targets. Additional post hoc analyses are compatible with the interpretation that saccade amplitudes and direction are computed in partial independence. Our experimental results indicate that task-induced modulations of saccade amplitudes reflect attentional modulations.
Molekulare Charakterisierung des Centrosom-assoziierten Proteins CP91 in Dictyostelium discoideum
(2016)
Das Dictyostelium-Centrosom ist ein Modell für acentrioläre Centrosomen. Es besteht aus einer dreischichtigen Kernstruktur und ist von einer Corona umgeben, welche Nukleationskomplexe für Mikrotubuli beinhaltet. Die Verdoppelung der Kernstruktur wird einmal pro Zellzyklus am Übergang der G2 zur M-Phase gestartet. Durch eine Proteomanalyse isolierter Centrosomen konnte CP91 identifiziert werden, ein 91 kDa großes Coiled-Coil Protein, das in der centrosomalen Kernstruktur lokalisiert. GFP-CP91 zeigte fast keine Mobilität in FRAP-Experimenten während der Interphase, was darauf hindeutet, dass es sich bei CP91 um eine Strukturkomponente des Centrosoms handelt. In der Mitose hingegen dissoziieren das GFP-CP91 als auch das endogene CP91 ab und fehlen an den Spindelpolen von der späten Prophase bis zur Anaphase. Dieses Verhalten korreliert mit dem Verschwinden der zentralen Schicht der Kernstruktur zu Beginn der Centrosomenverdopplung. Somit ist CP91 mit großer Wahrscheinlichkeit ein Bestandteil dieser Schicht. CP91-Fragmente der N-terminalen bzw. C-terminalen Domäne (GFP-CP91 N-Terminus, GFP-CP91 C-Terminus) lokalisieren als GFP-Fusionsproteine exprimiert auch am Centrosom, zeigen aber nicht die gleiche mitotische Verteilung des Volllängenproteins. Das CP91-Fragment der zentralen Coiled-Coil Domäne (GFP-CP91cc) lokalisiert als GFP-Fusionsprotein exprimiert, als ein diffuser cytosolische Cluster, in der Nähe des Centrosoms. Es zeigt eine partiell ähnliche mitotische Verteilung wie das Volllängenprotein. Dies lässt eine regulatorische Domäne innerhalb der Coiled-Coil Domäne vermuten. Die Expression der GFP-Fusionsproteine unterdrückt die Expression des endogenen CP91 und bringt überzählige Centrosomen hervor. Dies war auch eine markante Eigenschaft nach der Unterexpression von CP91 durch RNAi. Zusätzlich zeigte sich in CP91-RNAi Zellen eine stark erhöhte Ploidie verursacht durch schwere Defekte in der Chromosomensegregation verbunden mit einer erhöhten Zellgröße und Defekten im Abschnürungsprozess während der Cytokinese. Die Unterexpression von CP91 durch RNAi hatte auch einen direkten Einfluss auf die Menge an den centrosomalen Proteinen CP39, CP55 und CEP192 und dem Centromerprotein Cenp68 in der Interphase. Die Ergebnisse deuten darauf hin, dass CP91 eine zentrale centrosomale Kernkomponente ist und für den Zusammenhalt der beiden äußeren Schichten der Kernstruktur benötigt wird. Zudem spielt CP91 eine wichtige Rolle für eine ordnungsgemäße Centrosomenbiogenese und, unabhängig davon, bei dem Abschnürungsprozess der Tochterzellen während der Cytokinese.
Background: Aggression is a severe behavioral problem that interferes with many developmental challenges individuals face in middle childhood and adolescence. Particularly in the peer and in the academic domain, aggression inhibits the individual from making important learning experiences that are predictive for a healthy transition into adulthood. Furthermore, the resulting developmental deficits have the propensity to feedback and to promote aggression at later developmental stages. The aim of the present PhD thesis was to investigate pathways and processes involved in the etiology of aggression by examining the interrelation between multiple developmental problems in the peer and in the academic domain. More specifically, the relevance of affiliation with deviant peers as a driving mechanism for the development of aggression, factors promoting the affiliation with deviant peers (social rejection; academic failure), and mechanisms by which affiliation with deviant peers leads to aggression (external locus of control) were investigated.
Method: The research questions were addressed by three studies. Three data waves were available for the first study, the second and third study were based on two data waves. The first study specified pathways to antisocial behavior by investigating the temporal interrelation between social rejection, academic failure, and affiliation with deviant peers in a sample of 1,657 male and female children and adolescents aged between 6 and 15 years. The second study examined the role of external control beliefs as a potential mediator in the link between affiliation with deviant peers and aggression in a sample of 1,466 children and adolescents in the age of 9 to 19 years, employing a half-longitudinal design. The third study aimed to expand the findings of Study 1 and Study 2 by examining the differential predictivity of combinations of developmental risks for different functions of aggression, using a sample of 1,479 participants in the age between 9 and 19 years. First, profiles of social rejection, academic failure, and affiliation with deviant peers were identified, using latent profile analysis. Second, prospective pathways between risk-profiles and reactive and proactive aggression were investigated, using latent path analysis.
Results: The first study revealed that antisocial behavior at T1 was associated with social rejection and academic failure at T2. Both mechanisms promoted affiliation with deviant peers at the same data wave, which predicted deviancy at T3. Furthermore, both an indirect pathway via social rejection and affiliation with deviant peers and an indirect pathway via academic failure and affiliation with deviant peers significantly mediated the link between antisocial behavior at the first and the third data wave. Additionally, the proposed pathways generalized across genders and different age groups. The second study yielded that external control beliefs significantly mediated the link between affiliation with deviant peers and aggression, with affiliation with deviant peers at T1 predicting external control beliefs at T2 and external control beliefs at T1 predicting aggressive behavior at T2. Again, the analyses provided no evidence for gender and age specific variations in the proposed pathways. In the third study, three distinct risk groups were identified, made up of a large non-risk group, with low scores on all risk measures, a group characterized by high scores on social rejection (SR group), and a group with the highest scores on measures of affiliation with deviant peers and academic failure (APAF group). Importantly, risk group membership was differentially associated with reactive and proactive aggression. Only membership in the SR group at T1 was associated with the development of reactive aggression at T2 and only membership in the APAF group at T1 predicted proactive aggression at T2. Additionally, proactive aggression at T1 predicted membership in the APAF group at T2, indicating a reciprocal relationship between both constructs.
Conclusion: The results demonstrated that aggression causes severe behavioral deficits in social and academic domains which promote future aggression by increasing individuals’ tendency to affiliate with deviant peers. The stimulation of external control beliefs provides an explanation for deviant peers’ effect on the progression and intensification of aggression. Finally, multiple developmental risks were shown to co-occur within individuals and to be differentially predictive of reactive and proactive aggression. The findings of this doctoral dissertation have possible implications for the conceptualization of prevention and intervention programs aimed to reduce aggression in middle childhood and adolescence.
A majority of studies documented a reduced ankle muscle activity, particularly of the peroneus longus muscle (PL), in patients with functional ankle instability (FI). It is considered valid that foot orthoses as well as sensorimotor training have a positive effect on ankle muscle activity in healthy individuals and those with lower limb overuse injuries or flat arched feet (reduced reaction time by sensorimotor exercises; increased ankle muscle amplitude by orthoses use). However, the acute- and long-term influence of foot orthoses on ankle muscle activity in individuals with FI is unknown.
AIMS: The present thesis addressed (1a) acute- and (1b) long-term effects of foot orthoses compared to sensorimotor training on ankle muscle activity in patients with FI. (2) Further, it was investigated if the orthosis intervention group demonstrate higher ankle muscle activity by additional short-term use of a measurement in-shoe orthosis (compared to short-term use of “shoe only”) after intervention. (3) As prerequisite, it was evaluated if ankle muscle activity can be tested reliably and (4) if this differs between healthy individuals and those with FI.
METHODS: Three intervention groups (orthosis group [OG], sensorimotor training group [SMTG], control group [CG]), consisting of both, healthy individuals and those with FI, underwent one longitudinal investigation (randomised controlled trial). Throughout 6 weeks of intervention, OG wore an in-shoe orthosis with a specific “PL stimulation module”, whereas SMTG conducted home-based exercises. CG served to measure test-retest reliability of ankle muscle activity (PL, M. tibialis anterior [TA] and M. gastrocnemius medialis [GM]). Pre- and post-intervention, ankle muscle activity (EMG amplitude) was recorded during “normal” unperturbed (NW) and perturbed walking (PW) on a split-belt treadmill (stimulus 200 ms post initial heel contact [IC]) as well as during side cutting (SC), each while wearing “shoes only” and additional measurement in-shoe orthoses (randomized order). Normalized RMS values (100% MVC, mean±SD) were calculated pre- (100-50 ms) and post (200-400 ms) - IC.
RESULTS: (3) Test-retest reliability showed a high range of values in healthy individuals and those with FI. (4) Compared to healthy individuals, patients with FI demonstrated lower PL pre-activity during SC, however higher PL pre-activity for NW and PW. (1a) Acute orthoses use did not influence ankle muscle activity. (1b) For most conditions, sensorimotor training was more effective in individuals with FI than long-term orthotic intervention (increased: PL and GM pre-activity and TA reflex-activity for NW, PL pre-activity and TA, PL and GM reflex-activity for SC, PL reflex-activity for PW). However, prolonged orthoses use was more beneficial in terms of an increase in GM pre-activity during SC. For some conditions, long-term orthoses intervention was as effective as sensorimotor training for individuals with FI (increased: PL pre-activity for PW, TA pre-activity for SC, PL and GM reflex-activity for NW). Prolonged orthoses use was also advantageous in healthy individuals (increased: PL and GM pre-activity for NW and PW, PL pre-activity for SC, TA and PL reflex-activity for NW, PL and GM reflex-activity for PW). (2) The orthosis intervention group did not present higher ankle muscle activity by the additional short-term use of a measurement in-shoe orthosis at re-test after intervention.
CONCLUSION: High variations of reproducibility reflect physiological variability in muscle activity during gait and therefore deemed acceptable. The main findings confirm the presence of sensorimotor long-term effects of specific foot orthoses in healthy individuals (primary preventive effect) and those with FI (therapeutic effect). Neuromuscular compensatory feedback- as well as anticipatory feedforward adaptation mechanism to prolonged orthoses use, specifically of the PL muscle, underpins the key role of PL in providing essential dynamic ankle joint stability. Due to its advantages over sensorimotor training (positive subjective feedback in terms of comfort, time-and-cost-effectiveness), long-term foot orthoses use can be recommended as an applicable therapy alternative in the treatment of FI. Long-term effect of foot orthoses in a population with FI must be validated in a larger sample size with longer follow-up periods to substantiate the generalizability of the existing outcomes.
Inhalt
- Reinhard Andress: Ein unveröffentlichter Brief Alexander von Humboldts an den Buchhändler Jean-Georges Treuttel
- Julian Drews: Écriture (auto)biographique dans l‘Examen critique d‘Alexandre de Humboldt
- Alberto Gómez Gutiérrez: Alexander von Humboldt y la cooperación transcontinental en la Geografía de las plantas: una nueva apreciación de la obra fitogeográfica de Francisco José de Caldas
- Karin Reich und Elena Roussanova: Der Briefwechsel zwischen Karl Kreil und Alexander von Humboldt, ein wichtiger Beitrag zur Geschichte des Erdmagnetismus
- Alexander Stöger: Experiment und Wissensvermittlung. Alexander von Humboldts Darstellungsmethoden in seinen Versuchen über die gereizte Muskel- und Nervenfaser
- Friedrich Herneck und Ingo Schwarz: Friedrich Herneck: Hegel und Alexander von Humboldt
Alexander von Humboldt hat sich in jungen Jahren mit galvanischen Experimenten beschäftigt und die Resultate in einem umfassenden, zweibändigen Werk publiziert. Dabei zeigte er nicht nur, dass er als Experimentator und Teil der wissenschaftlichen Gemeinschaft fähig war, sich mit einem so neuen und komplexen Phänomen zu beschäftigen. Es lässt sich auch erkennen, dass er bereits in dieser frühen Schrift versuchte, das umfangreiche Wissen dem Leser zugänglich zu machen.
Der Artikel betrachtet Humboldts Galvanismusschrift Versuche über die gereizte Muskel- und Nervenfaser (1797–1798) und untersucht einige Elemente wie Anhänge und Schreibstil, die Humboldt nutzte, um die umfangreichen Informationen zu ordnen und dem Leser so neben den Big Data seiner Erkenntnisse auch passende Suchfunktionen zur Verfügung zu stellen, die eine gezielte Nutzung überhaupt ermöglichen.
Die Korrespondenz zwischen Alexander von Humboldt und Karl Kreil war umfangreich und betraf den Erdmagnetismus. Aber heute ist nur noch ein einziger Brief im Original bekannt. Dieser Brief, den Kreil am 3. September 1836 Alexander von Humboldt zukommen ließ, stimmt inhaltlich und teilweise wortwörtlich mit dem Brief überein, den Kreil nur einen Tag später, am 4. September 1836, an Carl Friedrich Gauß schickte. Vier Briefe von Kreil an Humboldt wurden in den „Annalen der Physik und Chemie“ publiziert, eine nicht allzu große Anzahl weiterer Briefe an Humboldt wurde in der biographischen Literatur über Kreil und in Briefen Kreils an Koller und Gauß erwähnt. Aber nicht nur die lückenhafte und bruchstückhaft bekannte Korrespondenz zwischen Humboldt und Kreil, die bis 1851 reicht, gibt Aufschluss über die Beziehungen, sondern von besonderer Bedeutung ist des Weiteren der Bestand an Kreiliana in der Bibliothek Humboldts. Es handelt sich um neun Werke Kreils, das letzte aus dem Jahr 1856. Nachweisbare Kontakte zwischen Kreil und Humboldt fanden also mit Sicherheit mindestens bis zu diesem Jahr statt!
El Ensayo sobre la geografía de las plantas de Alexander von Humboldt ha trascendido como una de sus principales propuestas científicas, fundamento de lo que se conoce hoy como “biogeografía”. El origen de este concepto es difuso hasta el momento de la publicación simultánea de su obra en París y en Tübingen, en 1807. El presente artículo propone contrastar la primera versión manuscrita de este ensayo, elaborada en 1803 en Guayaquil y luego leída en 1805 en el Institut National de Paris, con la obra contemporánea del neogranadino Francisco José de Caldas, con quien convivió en Quito en el primer semestre de 1802.
La référence à Colomb est un lieu commun de la biographie humboldtienne. Humboldt lui-même le souligne particulièrement dans son Examen critique, en y ajoutant une dimension autobiographique. La contribution analyse, dans une perspective philologique, le matériel et les formes de mise en scène avec lesquelles une vie est représentée au travers d'une autre.
Ein unveröffentlichter Brief Alexander von Humboldts an den Buchhändler Jean-Georges Treuttel
(2016)
In der Lilly Library der Indiana University befindet sich ein kurzer unveröffentlichter Brief Alexander von Humboldts an den Buchhändler und Autor Jean-Georges Treuttel. Dieser Artikel unternimmt den Versuch, den historisch-bibliographischen Kontext des Briefes herzustellen und ihn in Humboldts wissenschaftliches Schaffen einzuordnen.
The LEA (late embryogenesis abundant) proteins COR15A and COR15B from Arabidopsis thaliana are intrinsically disordered under fully hydrated conditions, but obtain α-helical structure during dehydration, which is reversible upon rehydration. To understand this unusual structural transition, both proteins were investigated by circular dichroism (CD) and molecular dynamics (MD) approaches. MD simulations showed unfolding of the proteins in water, in agreement with CD data obtained with both HIS-tagged and untagged recombinant proteins. Mainly intramolecular hydrogen bonds (H-bonds) formed by the protein backbone were replaced by H-bonds with water molecules. As COR15 proteins function in vivo as protectants in leaves partially dehydrated by freezing, unfolding was further assessed under crowded conditions. Glycerol reduced (40%) or prevented (100%) unfolding during MD simulations, in agreement with CD spectroscopy results. H-bonding analysis indicated that preferential exclusion of glycerol from the protein backbone increased stability of the folded state.
The interaction of water with α-alumina (i.e. α-Al2O3) surfaces is important in a variety of applications and a useful model for the interaction of water with environmentally abundant aluminosilicate phases. Despite its significance, studies of water interaction with α-Al2O3 surfaces other than the (0001) are extremely limited. Here we characterize the interaction of water (D2O) with a well defined α-Al2O3(1[1 with combining macron]02) surface in UHV both experimentally, using temperature programmed desorption and surface-specific vibrational spectroscopy, and theoretically, using periodic-slab density functional theory calculations. This combined approach makes it possible to demonstrate that water adsorption occurs only at a single well defined surface site (the so-called 1–4 configuration) and that at this site the barrier between the molecularly and dissociatively adsorbed forms is very low: 0.06 eV. A subset of OD stretch vibrations are parallel to this dissociation coordinate, and thus would be expected to be shifted to low frequencies relative to an uncoupled harmonic oscillator. To quantify this effect we solve the vibrational Schrödinger equation along the dissociation coordinate and find fundamental frequencies red-shifted by more than 1500 cm−1. Within the context of this model, at moderate temperatures, we further find that some fraction of surface deuterons are likely delocalized: dissociatively and molecularly absorbed states are no longer distinguishable.
In this work, three ligands produced from amino acids were synthesized and used to produce five bis- and PEPPSI-type palladium–NHC complexes using a novel synthesis route from sustainable starting materials. Three of these complexes were used as precatalysts in the aqueous-phase Suzuki–Miyaura coupling of various substrates displaying high activity. TEM and mercury poisoning experiments provide evidence for Pd-nanoparticle formation stabilized in water.
The synthesis and photophysical properties of two new FRET pairs based on coumarin as a donor and DBD dye as an acceptor are described. The introduction of a bromo atom dramatically increases the two-photon excitation (2PE) cross section providing a 2PE-FRET system, which is also suitable for 2PE-FLIM.
The aim of this study was to develop a one-step synthesis of gold nanotriangles (NTs) in the presence of mixed phospholipid vesicles followed by a separation process to isolate purified NTs. Negatively charged vesicles containing AOT and phospholipids, in the absence and presence of additional reducing agents (polyampholytes, polyanions or low molecular weight compounds), were used as a template phase to form anisotropic gold nanoparticles. Upon addition of the gold chloride solution, the nucleation process is initiated and both types of particles, i.e., isotropic spherical and anisotropic gold nanotriangles, are formed simultaneously. As it was not possible to produce monodisperse nanotriangles with such a one-step procedure, the anisotropic nanoparticles needed to be separated from the spherical ones. Therefore, a new type of separation procedure using combined polyelectrolyte/micelle depletion flocculation was successfully applied. As a result of the different purification steps, a green colored aqueous dispersion was obtained containing highly purified, well-defined negatively charged flat nanocrystals with a platelet thickness of 10 nm and an edge length of about 175 nm. The NTs produce promising results in surface-enhanced Raman scattering.
Optical biosensors based on porous silicon were fabricated by metal assisted chemical etching. Thereby double layered porous silicon structures were obtained consisting of porous pillars with large pores on top of a porous silicon layer with smaller pores. These structures showed a similar sensing performance in comparison to electrochemically produced porous silicon interferometric sensors.
In Near Edge X-Ray Absorption Fine Structure (NEXAFS) spectroscopy X-Ray photons are used to excite tightly bound core electrons to low-lying unoccupied orbitals of the system. This technique offers insight into the electronic structure of the system as well as useful structural information. In this work, we apply NEXAFS to two kinds of imidazolium based ionic liquids ([CnC1im]+[NTf2]- and [C4C1im]+[I]-). A combination of measurements and quantum chemical calculations of C K and N K NEXAFS resonances is presented. The simulations, based on the transition potential density functional theory method (TP-DFT), reproduce all characteristic features observed by the experiment. Furthermore, a detailed assignment of resonance features to excitation centers (carbon or nitrogen atoms) leads to a consistent interpretation of the spectra.
Herein we present an efficient synthesis of a biomimetic probe with modular construction that can be specifically bound by the mannose binding FimH protein – a surface adhesion protein of E. coli bacteria. The synthesis combines the new and interesting DBD dye with the carbohydrate ligand mannose via a Click reaction. We demonstrate the binding to E. coli bacteria over a large concentration range and also present some special characteristics of those molecules that are of particular interest for the application as a biosensor. In particular, the mix-and-measure ability and the very good photo-stability should be highlighted here.
Die vorgelegte Dissertation präsentiert wissenschaftliche Ergebnisse, die in der Zeit vom Dezember 2012 bis August 2016, erarbeitet wurden. Der zentrale Inhalt der Arbeit ist die Simulation von Röntgenabsorptionsprozessen von verschiedenen Systemen in kondensierter Phase. Genauer gesagt, werden Nahkantenabsorptions- (NEXAFS) sowie Röntgenphotoelektronenspektren (XPS) berechnet. In beiden Fällen wird ein Röntgenphoton von einem molekularen System absorbiert. Aufgrund der hohen Photonenenergie wird ein stark gebundenes kernnahes Elektron angeregt. Bei der XPS gelangt dieses mit einer zu messenden kinetischen Energie in Kontinuumszustände. In Abhängigkeit der eingestrahlten Photonenenergie und der kinetischen Energie des austreten Elektrons, kann die Bindungsenergie berechnet werden, welche die zentrale Größe der XPS ist. Im Falle der NEXAFS-Spektroskopie wird das kernnahe Elektron in unbesetzte gebundene Zustände angeregt. Die zentrale Größe ist die Absorption als Funktion der eingestrahlten Photonenenergie. Das erste Kapitel meiner Arbeit erörtert detailliert die experimentellen Methoden sowie die daraus gewonnenen charakteristischen Größen.
Die experimentellen Spektren zeigen oft viele Resonanzen, deren Interpretation aufgrund fehlender Referenzmaterialien schwierig ist. In solchen Fällen bietet es sich an, die Spektren mittels quantenchemischer Methoden zu simulieren. Der dafür erforderliche mathematisch-physikalische Methodenkatalog wird im zweiten Kapitel der Arbeit erörtert.
Das erste von mir untersuchte System ist Graphen. In experimentellen Arbeiten wurde die Oberfläche mittels Bromplasma modifiziert. Die im Anschluss gemessenen NEXAFS-Spektren unterscheiden sich maßgeblich von den Spektren der unbehandelten Oberfläche. Mithilfe periodischer DFT-Rechnungen wurden verschiedene Gitterdefekte sowie bromierte Systeme untersucht und die NEXAFS-Spektren simuliert. Mittels der Simulationen können die Beiträge verschiedener Anregungszentren analysiert werden. Die Berechnungen erlauben den Schluss, dass Gitterdefekte maßgeblich für die entstandenen Veränderungen verantwortlich sind.
Polyvinylalkohol (PVA) wurde als zweites System behandelt. Hierbei sollte untersucht werden, wie groß der Einfluss der Molekularbewegung auf die Verbreiterung der Peaks im XP-Spektrum ist. Des Weiteren wurde untersucht, wie groß der Einfluss von intermolekularen Wechselwirkungen auf die Peakpositionen und Peakverbreiterung ist. Für die Berechnung dieses Systems wurde eine Kombination aus molekulardynamischen und quantenchemischen Methoden verwendet. Als Strukturen dienten Oligomermodelle, die unter dem Einfluss eines (ab initio) Potentials propagiert wurden. Entlang der erstellten Trajektorie wurden Schnappschüsse der Geometrien extrahiert und für die Berechnung der XP-Spektren verwendet. Die Spektren werden bereits mithilfe klassischer Molekulardynamik sehr gut reproduziert. Die erhaltenen Peakbreiten sind verglichen mit dem Experiment allerdings zu klein. Die Hauptursache der Peakverbreiterung ist die Molekularbewegung. Intermolekulare Wechselwirkungen verschieben die Peakpositionen um 0.6 eV zu kleineren Anregungsenergien.
Im dritten Teil der Arbeit stehen die NEXAFS-Spektren von ionischen Flüssigkeiten (ILs) im Fokus. Die experimentell gefundenen Spektren zeigen eine komplexe Struktur mit vielen Resonanzen. In der Arbeit wurden zwei ILs untersucht. Als Geometrien verwenden wir Clustermodelle, die aus experimentellen Kristallstrukturen extrahiert wurden. Die berechneten Spektren erlauben es, die Resonanzen den Anregungszentren zuzuordnen. Außerdem kann eine erstmals gemessene Doppelresonanz simuliert und erklärt werden. Insgesamt kann die Interpretation der Spektren mithilfe der Simulation signifikant erweitert werden.
In allen Systemen wurde zur Berechnung des NEXAFS-Spektrums eine auf Dichtefunktionaltheorie basierende Methode verwendet (die sogenannte Transition-Potential Methode). Gängige wellenfunktionsbasierte Methoden, wie die Konfigurationswechselwirkung mit Einfachanregungen (CIS), zeigen eine starke Blauverschiebung, wenn als Referenz eine Hartree-Fock Slaterdeterminante verwendet wird. Wir zeigen, dass die Verwendung von kernnah-angeregten Determinanten sowohl das resultierende Spektrum als auch die Anregungsenergien deutlich verbessert. Des Weiteren werden auch Referenzen aus Dichtefunktionalrechnungen getestet. Zusätzlich werden auch Referenzen mit gebrochenen Besetzungszahlen für kernnahe Elektronen verwendet. In der Arbeit werden die Resultate der verschiedenen Referenzen miteinander verglichen. Es zeigt sich, dass Referenzen mit gebrochenen Besetzungszahlen das Spektrum nicht weiter verbessern. Der Einfluss der verwendeten Elektronenstrukturmethode ist eher gering.
Surface-enhanced Raman scattering (SERS) is a promising tool to obtain rich chemical information about analytes at trace levels. However, in order to perform selective experiments on individual molecules, two fundamental requirements have to be fulfilled. On the one hand, areas with high local field enhancement, so-called “hot spots”, have to be created by positioning the supporting metal surfaces in close proximity to each other. In most cases hot spots are formed in the gap between adjacent metal nanoparticles (NPs). On the other hand, the analyte has to be positioned directly in the hot spot in order to profit from the highest signal amplification. The use of DNA origami substrates provides both, the arrangement of AuNPs with nm precision as well as the ability to bind analyte molecules at predefined positions. Consequently, the present cumulative doctoral thesis aims at the development of a novel SERS substrate based on a DNA origami template. To this end, two DNA-functionalized gold nanoparticles (AuNPs) are attached to one DNA origami substrate resulting in the formation of a AuNP dimer and thus in a hot spot within the corresponding gap. The obtained structures are characterized by correlated atomic force microscopy (AFM) and SERS imaging which allows for the combination of structural and chemical information.
Initially, the proof-of principle is presented which demonstrates the potential of the novel approach. It is shown that the Raman signal of 15 nm AuNPs coated with dye-modified DNA
(dye: carboxytetramethylrhodamine (TAMRA)) is significantly higher for AuNP dimers arranged on a DNA origami platform in comparison to single AuNPs. Furthermore, by attaching single TAMRA molecules in the hot spot between two 5 nm AuNPs and optimizing the size of the AuNPs by electroless gold deposition, SERS experiments at the few-molecule level are presented. The initially used DNA origami-AuNPs design is further optimized in many respects. On the one hand, larger AuNPs up to a diameter of 60 nm are used which are additionally treated with a silver enhancement solution to obtain Au-Ag-core-shell NPs. On the other hand, the arrangement of both AuNPs is altered to improve the position of the dye molecule within the hot spot as well as to decrease the gap size between the two particles. With the optimized design the detection of single dye molecules (TAMRA and cyanine 3 (Cy3)) by means of SERS is demonstrated. Quantitatively, enhancement factors up to 10^10 are estimated which is sufficiently high to detect single dye molecules.
In the second part, the influence of graphene as an additional component of the SERS substrate is investigated. Graphene is a two-dimensional material with an outstanding combination of electronical, mechanical and optical properties. Here, it is demonstrated that
single layer graphene (SLG) replicates the shape of underlying non-modified DNA origami
substrates very well, which enables the monitoring of structural alterations by AFM imaging.
In this way, it is shown that graphene encapsulation significantly increases the structural
stability of bare DNA origami substrates towards mechanical force and prolonged exposure
to deionized water.
Furthermore, SLG is used to cover DNA origami substrates which are functionalized with a
40 nm AuNP dimer. In this way, a novel kind of hybrid material is created which exhibits
several advantages compared to the analogue non-covered SERS substrates. First, the fluorescence background of dye molecules that are located in between the AuNP surface and SLG is efficiently reduced. Second, the photobleaching rate of the incorporated dye molecules is decreased up to one order of magnitude. Third, due to the increased photostability of the investigated dye molecules, the performance of polarization-dependent series measurements on individual structures is enabled. This in turn reveals extensive information about the dye molecules in the hot spot as well as about the strain induced within the graphene lattice.
Although SLG can significantly influence the SERS substrate in the aforementioned ways, all
those effects are strongly related to the extent of contact with the underlying AuNP dimer.
Physikalische Hydrogele gewinnen derzeit als Zellsubstrate zunehmend an Interesse, da Viskoelastizität oder Stressrelaxation ein bedeutender Parameter in der Mechanotransduktion ist, der bisher vernachlässigt wurde. In dieser Arbeit wurden multi-funktionelle Polyurethane entworfen, die über einen neuartigen Gelierungsmechanismus physikalische Hydrogele bilden. In Wasser bilden die anionischen Polyurethane spontan Aggregate, welche durch elektrostatische Abstoßung in Lösung gehalten werden. Eine schnelle Gelierung kann von hier aus durch Ladungsabschirmung erreicht werden, wodurch die Aggregation voranschreitet und ein Netzwerk ausgebildet wird. Dies kann durch die Zugabe von verschiedenen Säuren oder Salzen geschehen, sodass sowohl saure (pH 4 - 5) als auch pH-neutrale Hydrogele erhalten werden können. Während konventionelle Hydrogele auf Polyurethan-Basis in der Regel durch toxische isocyanat-haltige Präpolymere hergestellt werden, eignet sich der hier beschriebene physikalische Gelierungsmechanismus für in situ Anwendungen in sensitiven Umgebungen. Sowohl Härte als auch Stressrelaxation der Hydrogele können unabhängig voneinander über einen breiten Bereich eingestellt werden. Darüberhinaus zeichnen sich die Hydrogele durch exzellente Stressregeneration aus.
Luhmann in da Contact Zone
(2016)
Our aim in this contribution is to productively engage with the abstractions and complexities of Luhmann’s conceptions of society from a postcolonial perspective, with a particular focus on the explanatory powers of his sociological systems theory when it leaves the realms of Europe and ventures to describe regions of the global South. In view of its more recent global reception beyond Europe, our aim is to thus – following the lead of Dipesh Chakrabarty – provincialize Luhmann’s system theory especially with regard to its underlying assumptions about a global “world society”. For these purposes, we intend to revisit Luhmann in the post/colonial contact zone: We wish to reread Luhmann in the context of spaces of transcultural encounter where “global designs and local histories” (Mignolo), where inclusion into and exclusion from “world society” (Luhmann) clash and interact in intricate ways. The title of our contribution, ‘Luhmann in da Contact Zone’ is deliberately ambiguous: On the one hand, we of course use ‘Luhmann’ metonymically, as representative of a highly complex theoretical design. We shall cursorily outline this design with a special focus on the notion of a singular, modern “world society”, only to confront it with the epistemic challenges of the contact zone. On the other hand, this critique will also involve the close observation of Niklas Luhman as a human observer (a category which within the logic of systems theory actually does not exist) who increasingly transpires in his late writings on exclusion in the global South. By following this dual strategy, we wish to trace an increasing fracture between one Luhmann and the other, between abstract theoretical design and personalized testimony. It is by exploring and measuring this fracture that we hope to eventually be able to map out the potential of a possibly more productive encounter between systems theory and specific strands of postcolonial theory for a pluritopic reading of global modernity.
Recollecting Bones
(2016)
In the same “guarded, roundabout and reticent way” which Lindsay Barrett invokes for Australian conversations about imperial injustice, Germans, too, must begin to more systematically explore, in Paul Gilroy’s words, “the connections and the differences between anti-semitism and anti-black and other racisms and asses[s] the issues that arise when it can no longer be denied that they interacted over a long time in what might be seen as Fascism’s intellectual, ethical and scientific pre-history” (Gilroy 1996: 26). In the meantime, we need to care for the dead. We need to return them, first, from the status of scientific objects to the status of ancestral human beings, and then progressively, and proactively, as close as possible to the care of those communities from whom they were stolen.
Kleine Kosmopolitismen
(2016)
Postcolonial Justice
(2016)