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Be Creative, Now!
(2018)
Purpose – This thesis set out to explore, describe, and evaluate the reality behind the rhetoric of freedom and control in the context of creativity. The overarching subject is concerned with the relationship between creativity, freedom, and control, considering freedom is also seen as an element of control to manage creativity.
Design/methodology/approach – In-depth qualitative data gathered from at two innovative start-ups. Two ethnographic studies were conducted. The data are based on participatory observations, interviews, and secondary sources, each of which included a three months field study and a total of 41 interviews from both organizations.
Findings – The thesis provides explanations for the practice of freedom and the control of creativity within organizations and expands the existing theory of neo-normative control. The findings indicate that organizations use complex control systems that allow a high degree of freedom that paradoxically leads to more control. Freedom is a cover of control, which in turn leads to creativity. Covert control even results in the responsibility to be creative outside working hours.
Practical implications – Organizations, which rely on creativity might use the results of this thesis. Positive workplace control of creativity provides both freedom and structure for creative work. While freedom leads to organizational members being more motivated and committing themselves more strongly to their and the organization’s goals, and a specific structure also helps to provide the requirements for creativity.
Originality/value – The thesis provides an insight into an approach to workplace control, which has mostly neglected in creativity research and proposes a modified concept of neo-normative control. It serves to provide a further understanding of freedom for creativity and to challenge the liberal claims of new control forms.
The aim of this doctoral thesis was to establish a technique for the analysis of biomolecules with infrared matrix-assisted laser dispersion (IR-MALDI) ion mobility (IM) spectrometry. The main components of the work were the characterization of the IR-MALDI process, the development and characterization of different ion mobility spectrometers, the use of IR-MALDI-IM spectrometry as a robust, standalone spectrometer and the development of a collision cross-section estimation approach for peptides based on molecular dynamics and thermodynamic reweighting.
First, the IR-MALDI source was studied with atmospheric pressure ion mobility spectrometry and shadowgraphy. It consisted of a metal capillary, at the tip of which a self-renewing droplet of analyte solution was met by an IR laser beam. A relationship between peak shape, ion desolvation, diffusion and extraction pulse delay time (pulse delay) was established. First order desolvation kinetics were observed and related to peak broadening by diffusion, both influenced by the pulse delay. The transport mechanisms in IR-MALDI were then studied by relating different laser impact positions on the droplet surface to the corresponding ion mobility spectra. Two different transport mechanisms were determined: phase explosion due to the laser pulse and electrical transport due to delayed ion extraction. The velocity of the ions stemming from the phase explosion was then measured by ion mobility and shadowgraphy at different time scales and distances from the source capillary, showing an initially very high but rapidly decaying velocity. Finally, the anatomy of the dispersion plume was observed in detail with shadowgraphy and general conclusions over the process were drawn.
Understanding the IR-MALDI process enabled the optimization of the different IM spectrometers at atmospheric and reduced pressure (AP and RP, respectively). At reduced pressure, both an AP and an RP IR-MALDI source were used. The influence of the pulsed ion extraction parameters (pulse delay, width and amplitude) on peak shape, resolution and area was systematically studied in both AP and RP IM spectrometers and discussed in the context of the IR-MALDI process. Under RP conditions, the influence of the closing field and of the pressure was also examined for both AP and RP sources. For the AP ionization RP IM spectrometer, the influence of the inlet field (IF) in the source region was also examined. All of these studies led to the determination of the optimal analytical parameters as well as to a better understanding of the initial ion cloud anatomy.
The analytical performance of the spectrometer was then studied. Limits of detection (LOD) and linear ranges were determined under static and pulsed ion injection conditions and interpreted in the context of the IR-MALDI mechanism. Applications in the separation of simple mixtures were also illustrated, demonstrating good isomer separation capabilities and the advantages of singly charged peaks. The possibility to couple high performance liquid chromatography (HPLC) to IR-MALDI-IM spectrometry was also demonstrated. Finally, the reduced pressure spectrometer was used to study the effect of high reduced field strength on the mobility of polyatomic ions in polyatomic gases.
The last focus point was on the study of peptide ions. A dataset obtained with electrospray IM spectrometry was characterized and used for the calibration of a collision cross-section (CCS) determination method based on molecular dynamics (MD) simulations at high temperature. Instead of producing candidate structures which are evaluated one by one, this semi-automated method uses the simulation as a whole to determine a single average collision cross-section value by reweighting the CCS of a few representative structures. The method was compared to the intrinsic size parameter (ISP) method and to experimental results. Additional MD data obtained from the simulations was also used to further analyze the peptides and understand the experimental results, an advantage with regard to the ISP method. Finally, the CCS of peptide ions analyzed by IR-MALDI were also evaluated with both ISP and MD methods and the results compared to experiment, resulting in a first validation of the MD method. Thus, this thesis brings together the soft ionization technique that is IR-MALDI, which produces mostly singly charged peaks, with ion mobility spectrometry, which can distinguish between isomers, and a collision cross-section determination method which also provides structural information on the analyte at hand.
Ab 1806 versuchte Napoleon über sieben Jahre hinweg, den europäischen Kontinent gegen jegliche Importe aus Großbritannien abzuschotten. Dieses protektionistische Großexperiment löste in der zeitgenössischen Presse intensive Debatten zu wirtschaftstheoretischen Fragen aus: Fördert ökonomischer Isolationismus den nationalen Wohlstand? Können internationale Rechtsregelungen einem Handelskrieg entgegenwirken? Oder werden nationaler Wohlstand und damit globaler Frieden nicht eher durch allgemeinen Freihandel begünstigt? Alix Winter stellt das wirtschaftspolitische Ereignis der Kontinentalsperre als Kristallisationspunkt öffentlicher Auseinandersetzungen über ökonomische Grundsatzfragen heraus und identifiziert das frühe 19. Jahrhundert als Radikalisierungsphase aufklärerischer liberaler Wirtschaftstheorien.In 1806, Napoleon attempted to seal off the entire European continent from British imports. This ambitious protectionist experiment set off extensive debates about questions of economic theory. Did economic isolation foster the wealth of nations? Could international law prevent the outbreak of a maritime trade war? Or would global free trade promote wealth and peace among all nations? In this book, Alix Winter studies how the continental system served as a focal point for public discussions about fundamental economical questions and how the early nineteenth century witnessed the radicalisation of Enlightenment liberal economic theories.
Im Fokus der bildungshistorischen und doppelbiografischen Dissertation steht die Darstellung des vielseitigen Reformengagements der Torhorst-Schwestern Adelheid und Marie im (Aus-) Bildungswesen der Weimarer Republik. Die Begriffe „Reform“ und „Engagement“ stellen tragende inhaltliche Signaturen der quellenbasierten Annäherung an das Geschwisterpaar dar. Thematisiert werden ihre Berufsbiografien in ihren jeweiligen bildungspolitischen sowie bildungspraktischen Wirkungskreisen – inmitten der ersten „echten“ deutschen Demokratie. Die Studie zielt insbesondere darauf ab, den Kreis der bildungshistorischen Repräsentantinnen für eine konstruktive Ausgestaltung des (Fort-)Bildungswesens im Sinne eines notwendigen, aber nicht realisierten Modernisierungs- und Demokratisierungsprozesses in jenem Zeitraum zu erweitern. Die Aufarbeitung des bisher in der bildungsgeschichtlichen Forschung weitestgehend unbekannten Schaffens vermag es, den vielschichtigen Bedeutungsebenen von Schulreform(en) und Reformpädagogik gerecht(er) zu werden. Die Arbeit intendiert zudem eine Horizonterweiterung des bildungshistorischen Blickfeldes – vor allem in Bezug auf bildungspolitische und schulpraktische Realisierungen von essenziellen Reformen in den Bereichen sekundärer (Aus-)Bildungseinrichtungen.
Die Schwestern bestimmten sowohl als kommunalpolitische als auch als schulpraktische Akteure die neue Praxis und die neuen Anforderungen der demokratischen Staatsform mit. Adelheid Torhorst kämpfte – über ihren kommunalen Verantwortungsradius hinausreichend – aktiv im Rahmen ihrer von 1924–1931 andauernden Mitgliedschaft im Bund der Freien Schulgesellschaften (BFS) für eine gesamte Weltlichkeit des deutschen Schul- und (Aus-)Bildungswesens. Beide Frauen mussten auf ihren Tätigkeitsebenen erfahren, dass ihre immer stärker werdenden sozialistisch geprägten Vorstellungen bezüglich der deutschen Bildungslandschaft Illusionen blieben. Vielmehr erkannten sie zunehmend einen Zusammenhang zwischen den etablierten Machtstrukturen; ein gesellschaftlicher Fortschritt, der sich in ihren Augen in einem sozial durchlässigen und weltlichen Bildungswesen formierte, erforderte vor allem strukturelle Veränderungen. Für diese jedoch gab es keine gesellschaftlichen und politischen Mehrheiten.
Die doppelbiografische Perspektive mit dem Fokus auf das Bleibende des Reformengagements sensibilisiert für gegenwärtige bildungspolitische Streitfragen. Der kritisch-reflexive Blick geht zunächst mit einer Würdigung der qualifizierenden deutschen (Aus-) Bildungslandschaft einher; schätzt die liberalen Errungenschaften wie die Entscheidungsfreiheit der Eltern in Bezug zum Besuch des Religionsunterrichts ihrer Kinder als ein Privileg einer demokratischen, sozial offenen Gesellschaft. Es braucht in einer herausfordernden Zukunft mehr denn je mutige Akteure mit progressivem Reformpotenzial. Das wegweisende Engagement der Torhorst-Schwestern stand im Kontext eines schulischen sowie gesellschaftlichen Fortschrittgedankens, der sowohl die Moderne positiv prägt und trägt, der aber auch für deren Krisen und Konflikte steht. Im gegenwärtigen (Aus-)Bildungswesen entstehen ebenso immer wieder neue Spannungen und Reformbedarfe, die es gilt, mit entsprechenden bildungspolitischen Richtlinien „von oben“ gesetzlich neu zu reglementieren – mit Leben gefüllt werden sie mit dem Engagement „von unten“.
Nervous allies
(2018)
Diese Dissertation untersucht die Entwicklung der diplomatischen Beziehungen zwischen Frankreich, den USA und der Bundesrepublik Deutschland im Zeitraum von 1969-1980. Auf breiter multiarchivarischer Quellengrundlage rekonstruiert sie die interdependente Außenpolitik dieser drei Staaten im Kontext zentraler Themenkomplexe der 1970er Jahre: des Aufstiegs und Verfalls der Entspannungspolitik, des Streits um den Status quo in Europa, die Deutsche Frage und die Zukunft Berlins, der internationalen Wirtschafts- und Währungskrise, der Debatte um Sicherheit und Zukunft des westlichen Bündnisses und des NATO-Doppelbeschlusses. Ebenso betrachtet werden eine Reihe von regionalen Ereignissen und Konflikten mit weitreichenden Auswirkungen wie der Jom-Kippur-Krieg, die Portugiesische Revolution oder die sowjetische Invasion Afghanistans.
Die Untersuchung folgt der zentralen, theoretisch motivierten Fragestellung, in welchem Maß staatliche Außenpolitik und diplomatische Beziehungen von individuellen Akteuren an der Spitze der Regierungen, ihren Agenden, Sichtweisen und persönlichen Beziehungen zu internationalen Partnern geprägt wurden oder in welchem Maß deren Entscheidungsfindung andererseits durch strukturelle Faktoren geopolitischer, ökonomischer oder politischer Natur definiert und limitiert wurde. Um diese Frage zu beantworten, fokussiert sich die Dissertation auf die Analyse von Regierungswechseln und deren Auswirkungen auf Kontinuität und Wandel der Außenpolitik. Die Narrative umfasst sieben solcher Regierungswechsel: von Bundeskanzler Kurt Georg Kiesinger zu Willy Brandt (1969) und von Brandt zu Helmut Schmidt (1974) in Bonn, von Präsident Charles de Gaulle zu Georges Pompidou (1969) und von Pompidou zu Valéry Giscard d’Estaing (1974) in Paris sowie von Lyndon B. Johnson zu Richard M. Nixon (1969), von Nixon zu Gerald R. Ford (1974) und von Ford zu Jimmy Carter (1977) in Washington.
Abseits eines Spektrums empirisch fundierter Erkenntnisse über die Geschichte der internationalen Beziehungen der 1970er Jahre belegt diese Arbeit vor allem hochgradig personalisierte und exklusive außenpolitische Entscheidungsstrukturen und eine deutliche Abhängigkeit der Qualität intergouvernementaler Beziehungen von den persönlichen Beziehungen außenpolitischer Führungspersönlichkeiten. Zugleich werden jedoch strukturelle Grenzen ihres Handlungsspielraums im internationalen System deutlich, die von Faktoren wie militärischer Sicherheit und geopolitischer Lage, Zugang zu Ressourcen und ökonomischer Leistungsfähigkeit sowie politischem Druck aus dem In- und Ausland abhängen. Die Dissertation kommt zu dem zentralen Ergebnis, dass Regierungswechsel zwar bisweilen drastische Einschnitte in Inhalt und Stil der auswärtigen Beziehungen nach sich zogen und Bonn, Paris und Washington im Laufe der Dekade mit vielerlei neuen Herausforderungen konfrontiert wurden, dass in der Gesamtschau jedoch pfadabhängige strukturelle Druckszenarien zu höherer politischer Kontinuität im internationalen System führten, als oft mit den für tiefgreifenden historischen Wandel bekannten 1970er Jahren assoziiert wird.
Systemic inflammation is a hallmark of cancer cachexia. Among tumor-host interactions, the white adipose tissue (WAT) is an important contributor to inflammation as it suffers morphological reorganization and lipolysis, releasing free fatty acids (FA), bioactive lipid mediators (LM) and pro-inflammatory cytokines, which accentuate the activation of pro-inflammatory signaling pathways and the recruitment of immune cells to the tissue. This project aimed to investigate which inflammatory factors are involved in the local adipose tissue inflammation and what is the influence of such factors upon enzymes involved in FA or LM metabolism in healthy individuals (Control), weight stable gastro-intestinal cancer patients (WSC) and cachectic cancer patients (CC). The results demonstrated that the inflammatory signature of systemic inflammation is different from local adipose tissue inflammation. The systemic inflammation of the cachectic cancer patients was characterized by higher levels of circulating saturated fatty acids (SFA), tumor-necrosis-factor-α (TNF-α), interleukins IL-6, IL-8 and CRP while levels of polyunsaturated fatty acids (PUFAs), especially n3-PUFAs, were lower in CC than in the other groups. In vitro and in adipose tissue explants, pro-inflammatory cytokines and SFAs were shown to increase the chemokines IL-8 and CXCL10 that were found to be augmented in adipose tissue inflammation in CC which was more profound in the visceral adipose tissue (VAT) than in subcutaneous adipose tissue (SAT). Systemic inflammation was negatively associated with the expression of PUFA synthesizing enzymes, though gene and protein expression did hardly differ between groups. The effects of inflammatory factors on enzymes in the whole tissue could have been masked by differentiated modulation of the diverse cell types in the same tissue. In vitro experiments showed that the expression of FA-modifying enzymes such as desaturases and elongases in adipocytes and macrophages was regulated into opposing directions by TNF-α, IL-6, LPS or palmitate. The higher plasma concentration of the pro-resolving LM resolvin D1 in CC cannot compensate the overall inflammatory status and the results indicate that inflammatory cytokines interfere with synthesis pathways of pro-resolving LM. In summary, the data revealed a complex inter-tissue and inter-cellular crosstalk mediated by pro-inflammatory cytokines and lipid compounds enhancing inflammation in cancer cachexia by feed-forward mechanisms.
The solar activity and its consequences affect space weather and Earth’s climate. The solar activity exhibits a cyclic behaviour with a period of about 11 years. The solar cycle properties are governed by the dynamo taking place in the interior of the Sun, and they are distinctive. Extending the knowledge about solar cycle properties into the past is essential for understanding the solar dynamo and forecasting space weather. It can be acquired through the analysis of historical sunspot drawings. Sunspots are the dark areas, which are associated with strong magnetic fields, on the solar surface. Sunspots are the oldest and longest available observed features of solar activity.
One of the longest available records of sunspot drawings is the collection by Samuel Heinrich Schwabe during 1825–1867. The sunspot sizes measured from digitized Schwabe drawings are not to scale and need to be converted into physical sunspot areas. We employed a statistical approach assuming that the area distribution of sunspots was the same in the 19th century as it was in the 20th century. Umbral areas for about 130 000 sunspots observed by Schwabe were obtained. The annually averaged sunspot areas correlate reasonably well with the sunspot number. Tilt angles and polarity separations of sunspot groups were calculated assuming them to be bipolar. There is, of course, no polarity information in the observations. We derived an average tilt angle by attempting to exclude unipolar groups with a minimum separation of the two surmised polarities and an outlier rejection method, which follows the evolution of each group and detects the moment, when it turns unipolar as it decays. As a result, the tilt angles, although displaying considerable natural scatter, are on average 5.85° ± 0.25°, with the leading
polarity located closer to the equator, in good agreement with tilt angles obtained from 20th century data sets. Sources of uncertainties in the tilt angle determination are discussed and need to be addressed whenever different data sets are combined.
Digital images of observations printed in the books Rosa Ursina and Prodromus pro sole mobili by Christoph Scheiner, as well as the drawings from Scheiner’s letters to Marcus Welser, are analyzed to obtain information on the positions and sizes of sunspots that appeared before the Maunder minimum. In most cases, the given orientation of the ecliptic is used to set up the heliographic coordinate system for the drawings. Positions and sizes are measured manually displaying the drawings on a computer screen. Very early drawings have no indication of the solar orientation. A rotational matching using common spots of adjacent days is used in some cases, while in other cases, the assumption that images were aligned with a zenith–horizon coordinate system appeared to be the most likely. In total, 8167 sunspots were measured. A distribution of sunspot latitudes versus time (butterfly diagram) is obtained for Scheiner’s observations. The observations of 1611 are very inaccurate, but the drawings of 1612 have at least an indication of the solar orientation, while the remaining part of the spot positions from 1618–1631 have good to very good accuracy. We also computed 697 tilt angles of apparent bipolar sunspot groups, which were observed in the period 1618–1631. We find that the average tilt angle of nearly 4° does not significantly differ from the 20th century values.
The solar cycle properties seem to be related to the tilt angles of sunspot groups, and it is an important parameter in the surface flux transport models. The tilt angles of bipolar sunspot groups from various historical sets of solar drawings including from Schwabe and Scheiner are analyzed. Data by Scheiner, Hevelius, Staudacher, Zucconi, Schwabe, and Spörer deliver a series of average tilt angles spanning a period of 270 years, in addition to previously found values for 20th-century data obtained by other authors. We find that the average tilt angles before the Maunder minimum were not significantly different from modern values. However, the average tilt angles of a period 50 years after the Maunder minimum, namely for cycles 0 and 1, were much lower and near zero. The typical tilt angles before the Maunder minimum suggest that abnormally low tilt angles were not responsible for driving the solar cycle into a grand minimum.
With the Schwabe (1826–1867) and Spörer (1866–1880) sunspot data, the butterfly diagram of sunspot groups extends back till 1826. A recently developed method, which separates the wings of the butterfly diagram based on the long gaps present in sunspot group occurrences at different latitudinal bands, is used to separate the wings of the butterfly diagram. The cycle-to-cycle variation in the start (F), end (L), and highest (H) latitudes of the wings with respect to the strength of the wings are analyzed. On the whole, the wings of the stronger cycles tend to start at higher latitudes and have a greater extent. The time spans of the wings and the time difference between the wings in the northern hemisphere display a quasi-periodicity of 5–6 cycles. The average wing overlap is zero in the southern hemisphere, whereas it is 2–3 months in the north. A marginally significant oscillation of about 10 solar cycles is found in the asymmetry of the L latitudes. This latest, extended database of butterfly wings provides new observational constraints, regarding the spatio-temporal distribution of sunspot occurrences over the solar cycle, to solar dynamo models.
This thesis investigates the comprehension of the passive voice in three distinct populations. First, the comprehension of passives by adult German speakers was studied, followed by an examination of how German-speaking children comprehend the structure. Finally, bilingual Mandarin-English speakers were tested on their comprehension of the passive voice in English, which is their L2. An integral part of testing the comprehension in all three populations is the use of structural priming. In each of the three distinct parts of the research, structural priming was used for a specific reason. In the study involving adult German speakers, productive and receptive structural priming was directly compared. The goal was to see the effect the two priming modalities have on language comprehension. In the study on German-acquiring children, structural priming was an important tool in answering the question regarding the delayed acquisition of the passive voice. Finally, in the study on the bilingual population, cross-linguistic priming was used to investigate the importance of word order in the priming effect, since Mandarin and English have different word orders in passive voice sentences.
Modeling and data analysis of large-scale atmosphere dynamics associated with extreme weather
(2018)
In the last decades the frequency and intensity of extreme weather events like heat waves and heavy rainfall have increased and are at least partly linked to global warming. These events can have a strong impact on agricultural and economic production and, thereby, on society. Thus, it is important to improve our understanding of the physical processes leading to those extreme events in order to provide accurate near-term and long-term forecasts. Thermodynamic drivers associated with global warming are well understood, but dynamical aspects of the atmosphere much less so. The dynamical aspects, while less important than the thermodynamic drivers in regards to large-scale and long-time averaged effects, play a critical role in the formation of extremes.
The overall aim of this thesis is to improve our understanding of patterns, variability and trends in the global atmospheric circulation under a changing climate. In particular, in this dissertation I developed two new data-driven methods to quantitatively describe the dynamics of jet streams, Hadley cells and storm tracks. In addition, I introduce and validate a new statistical-dynamical atmosphere model that can be used to efficiently model the large-scale circulation.
First, I developed a scheme based on the Dijkstra ‘shortest-path’ algorithm to identify jet stream cores. Using reanalysis data, I found a significant change in jet stream strength and position over the last decades: Specifically, a decrease in wind speeds and a spatial shift toward the poles. This work also shows that the splitting or merging of the polar front jet stream and the subtropical jet stream depends on the season and longitudinal position. In a follow-up study, I analyzed trends in the latitudinal position of the poleward edge of the Hadley cell and subtropical jet stream core for all longitudes. These trends depend strongly on longitude and thus the impacts of tropical expansion might be pronounced in some regions and absent in others.
The second approach was to develop an empirical forecast method for European and Mediterranean winter precipitation. This prediction algorithm innovatively incorporates the spatial patterns of predictors in autumn using clustering analyses. I identified the most important precursors (snow cover in Eurasia, Barents and Kara sea ice concentrations as well as sea surface temperature in the Atlantic and Mediterranean region) for the precipitation prediction. This forecast algorithm had higher forecast skills than conventionally employed methods such as Canonical Correlation Analysis or operational systems using climate models.
The last approach was to examine the atmospheric circulation using the novel statisticaldynamical atmosphere model Aeolus. First, I validated the model’s depiction of the largescale circulation in terms of Hadley circulation, jet streams, storm tracks and planetary waves. To do so, I performed a parameter optimization using simulated annealing. Next, I investigated the sensitivity of the large-scale circulation to three different temperature components: global mean temperature, meridional temperature gradient and zonal temperature gradient. The model experiment showed that the strength of the Hadley cell, storm tracks and jet streams depend almost linearly on both the global mean temperature and the meridional temperature gradient, whereas the zonal temperature gradient is shown to have little or no influence. The magnitude of planetary waves is clearly affected by all three temperature components. Finally, the width of the Hadley cell behaves nonlinearly with respect to all three temperature components.
These findings might have profound consequences for climate modeling of the Mediterranean region. The latitudinal poleward trend of the Hadley cell edge position might become stronger under climate change according to the results with Aeolus. These changes would lead to a substantial reduction of the winter precipitation in the Mediterranean region. In this case seasonal empirical forecast methods, like the clustering-based prediction scheme, will play an important role for forecasting seasonal droughts in advance such that water managers and politicians can mitigate impacts.
The ongoing trend of miniaturizing multifunctional devices, especially for minimally-invasive medical or sensor applications demands new strategies for designing the required functional polymeric micro-components or micro-devices. Here, polymers, which are capable of active movement, when an external stimulus is applied (e.g. shape-memory polymers), are intensively discussed as promising material candidates for realization of multifunctional micro-components. In this context further research activities are needed to gain a better knowledge about the underlying working principles for functionalization of polymeric micro-scale objects with a shape-memory effect. First reports about electrospun solid microfiber scaffolds, demonstrated a much more pronounced shape-memory effect than their bulk counterparts, indicating the high potential of electrospun micro-objects.
Based on these initial findings this thesis was aimed at exploring whether the alteration of the geometry of micro-scale electrospun polymeric objects can serve as suitable parameter to tailor their shape-memory properties. The central hypothesis was that different geometries should result in different degrees of macromolecular chain orientation in the polymeric micro-scale objects, which will influence their mechanical properties as well as thermally-induced shape-memory function. As electrospun micro-scale objects, microfiber scaffolds composed of hollow microfibers with different wall thickness and electrosprayed microparticles as well as their magneto-sensitive nanocomposites all prepared from the same polymer exhibiting pronounced bulk shape-memory properties were investigated. For this work a thermoplastic multiblock copolymer, named PDC, with excellent bulk shape-memory properties, associated with crystallizable oligo(ε-caprolactone) (OCL) switching domains, was chosen for the preparation of electrospun micro-scale objects, while crystallizable oligo(p-dioxanone) (OPDO) segments serve as hard domains in PDC.
In the first part of the thesis microfiber scaffolds with different microfiber geometries (solid or hollow with different wall thickness) were discussed. Hollow microfiber based PDC scaffolds were prepared by coaxial electrospinning from a 1, 1, 1, 3, 3, 3 hexafluoro-2-propanol (HFP) solution with a polymer concentration of 13% w·v-1. Here as a first step core-shell fiber scaffolds consisting of microfibers with a PDC shell and sacrificial poly(ethylene glycol) (PEG) core are generated. The hollow PDC microfibers were achieved after dissolving the PEG core with water. The utilization of a fixed electrospinning setup and the same polymer concentration of the PDC spinning solution could ensure the fabrication of microfibers with almost identical outer diameters of 1.4 ± 0.3 µm as determined by scanning electron microscopy (SEM). Different hollow microfiber wall thicknesses of 0.5 ± 0.2 and 0.3 ± 0.2 µm (analyzed by SEM) have been realized by variation of the mass flow rate, while solid microfibers were obtained by coaxial electrospinning without supplying any core solution. Differential scanning calorimetry experiments and tensile tests at ambient temperature revealed an increase in degree of OCL crystallinity form χc,OCL = 34 ± 1% to 43 ± 1% and a decrease in elongation of break from 800 ± 40% to 200 ± 50% associated with an increase in Young´s modulus and failture stress for PDC hollow microfiber scaffolds when compared with soild fibers. The observed effects were enhanced with decreasing wall thickness of the single hollow fibers. The shape-memory properties of the electrospun PDC scaffolds were quantified by cyclic, thermomechanical tensile tests. Here, scaffolds comprising hollow microfibers exhibited lower shape fixity ratios around Rf = 82 ± 1% and higher shape recovery ratios of Rr = 67 ± 1% associated to more pronounced relaxation at constant strain during the first test cycle and a lower switching temperature of Tsw = 33 ± 1 °C than the fibrous meshes consisting of solid microfibers. These findings strongly support the central hypothesis that different fiber geometries (solid or hollow with different wall thickness) in electrospun scaffolds result in different degrees of macromolecular chain orientation in the polymeric micro-scale objects, which can be applied as design parameter for tailoring their mechanical and shape-memory properties.
The second part of the thesis deals with electrosprayed particulate PDC micro-scale objects. Almost spherical PDC microparticles with diameters of 3.9 ± 0.9 μm (as determined by SEM) were achieved by electrospraying of HFP solution with a polymer concentration of 2% w·v-1. In contrast, smaller particles with sizes of 400 ± 100 nm or 1.2 ± 0.3 μm were obtained for the magneto-sensitive composite PDC microparticles containing 23 ± 0.5 wt% superparamagnetic magnetite nanoparticles (mNPs). All prepared PDC microparticles exhibited a similar overall crystallinity like the PDC bulk material as analyzed by DSC. AFM nanoindentation results revealed no influence of the nanofiller incorporation on the local mechanical properties represented by the reduced modulus determined for pure PDC microparticles and magneto-sensitive composite PDC microparticles with similar diameters around 1.3 µm. It was found that the reduced modulus of the nanocomposite microparticles increased substantially with decreasing particles size from 2.4 ± 0.9 GPa (1.2 µm) to 11.9 ± 3.1 GPa (0.4 µm), which can be related to a higher orientation of the macromolecules at the surface of smaller sized microparticles. The magneto-sensitivity of such nanocomposite microparticles could be demonstrated in two aspects. One was by attracting/collecting the composite micro-objects with an external permanent magnet. The other one was by a inductive heating to 44 ± 1 °C, which is well above the melting transition of the OCL switching domains, when compacted to a 10 x 10 mm2 film with a thickness of 10 µm and exposed to an alternating magnet field with an magnetic field strength of 30 kA·m-1. Both functions are of great relevance for designing next generation drug delivery systems combining targeting and on demand release.
By a compression approach shape-memory functionalization of individual microparticles could be realized. Here different programming pressures and compression temperatures were applied. The shape-recovery capability of the programmed PDC microparticles was quantified by online and off-line heating experiments analyzed via microscopy measurement. The obtained shape-memory properties were found to be strongly depending on the applied programming pressure and temperature. The best shape-memory performance with a high shape recovery rate of about Rr = 80±1% was obtained when a low pressure of 0.2 MPa was applied at 55 °C. Finally, it was demonstrated that PDC microparticles can be utilized as micro building parts for preparation of a macroscopic film with temporary stability by compression of a densely packed array of PDC microparticles at 60 °C followed by subsequent cooling to ambient temperature. This film disintegrates into individual microparticles upon heating to 60 °C. Based on this technology the design of stable macroscopic release systems can be envisioned, which can be easily fixed at the site of treatment (i.e. by suturing) and disintegrate on demand to microparticles facilitating the drug release.
In summary, the results of this thesis could confirm the central hypothesis that the variation of the geometry of polymeric micro-objects is a suitable parameter to adjust their shape-memory performance by changing the degree of macromolecular chain orientation in the specimens or by enabling new functions like on demand disintegration. These fundamental findings might be relevant for designing novel miniaturized multifunctional polymer-based devices.
La cabrona aquí soy yo
(2018)
La última década ha visto un interés creciente en el fenómeno del narcotráfico en México a nivel global. Las diversas expresiones de violencia extrema que acompañan al negocio ilegal de drogas se narran en artefactos mediáticos que provocan fascinación e intriga. Así, la literatura y el cine, la música y la televisión presentan imágenes e historias sobre el narcotráfico que alimentan el imaginario colectivo.
En este contexto, a nivel global hay representaciones mediáticas de la mujer mexicana narcotraficante que reproducen estereotipos femeninos donde la mujer se cosifica, exagerando los atributos sexuales del cuerpo de las mujeres. Esta representación cultural hace de la mujer un objeto de deseo, cuya belleza sirve como una marca de prestigio y ostentación para el hombre narcotraficante. La cultura del narcotráfico impone a las mujeres un ideal estético particular distintivo, que las mujeres reproducen meticulosamente para emular esta representación. Aunado a la belleza física, la mujer es retratada violenta y sin escrúpulos, usa su belleza y poder de seducción para acumular dinero y poder a costa de los hombres que conquista. Para los que no pertenecen al mundo del narcotráfico, este tipo de mujer, hipersexualizada, inspira juicios negativos, discriminación, desconfianza y temor.
La intención de la pregunta y objetivos de investigación de este trabajo fue rebasar estas representaciones para observar las complejidades de las experiencias de vida de estas mujeres. El propósito de esta tesis de doctorado fue explorar cómo cambian las vidas de las mujeres mexicanas cuando se involucran en la narcocultura, en la frontera México-Estados Unidos. En específico, la investigación analizó las transformaciones en la corporalidad y en las subjetividades de estas mujeres, y cómo estas transformaciones influían en el lugar que ocupan en el espacio social y cultural que configura el narcotráfico. Además, se analizó qué márgenes de negociación tienen las mujeres en la narcocultura, para poder actuar y definirse a sí mismas.
Las preguntas que guiaron el trabajo indagaban sobre cómo las mujeres cambiaban su cuerpo para encarnar el ideal estético y qué significados se atribuían a estos cambios. Fue importante analizar qué dinámicas de poder se ponían en juego a partir de estos cuerpos femeninos, en las relaciones con los hombres y con otras mujeres. También, otro objetivo fue qué procesos de subjetivación operaban en las mujeres que participan en la narcocultura, y qué márgenes de negociación tenían para actuar y definirse a sí mismas.
Esta es una investigación inscrita dentro de los estudios culturales y con una perspectiva feminista interseccional. La investigación se realizó en la frontera mexicana con Estados Unidos, en el noroeste, específicamente en las ciudades de Mexicali, Tijuana y San Diego, California. La frontera, en esta tesis, se observa como un espacio con múltiples contextos de interpretación, polisémico y heterogéneo. Estas cualidades hacen que los fenómenos culturales que ocurren en él sean diversos y contradictorios.
Para entender los fenómenos culturales que emergen de la frontera norte de México, fue útil el concepto de transfrontera de José Valenzuela Arce (2014). La propuesta de este académico es que las transfronteras son “espacios que se niegan a una sola de las condiciones o los lados que la integran” (p. 9). Así, el concepto habla de los procesos de conectividad y simultaneidad que la globalización genera y que redefinen a los Estados-territorio. Al mismo tiempo, habla también de los límites que estos mismos Estados utilizan para sostener narrativas nacionales que son “referentes organizadores de adscripciones identitarias y culturales” (p. 18) que crean diferencias y desigualdades. Si esto es así, una frontera no se explica completamente desde la demarcación territorial o desde la diferenciación jerárquica que incluye a algunos y excluye a otros, pero tampoco puede entenderse si nos concentramos solamente en los procesos de hibridación cultural que ocurren en esos espacios. Por eso, para Valenzuela las fronteras son entre espacios y entre tiempos.
Este concepto ayuda a entender cómo se intersecta lo global y local en los sistemas semióticos que componen el universo cultural del narcotráfico mexicano, al mismo tiempo que explica cómo se estructuran mecanismos de exclusión y jerarquías a partir del género, la posición social y otras marcas de diferenciación social. En última instancia, ayuda a localizar estos procesos culturales, materializados en el cuerpo de las mujeres.
El concepto de narcocultura también fue una herramienta heurística útil. La cultura aquí se entiende como un proceso de producción y reproducción de modelos simbólicos, materializados en artefactos o representaciones y, además, interiorizados en lógicas de vida, sistemas de valores y creencias, que circulan a través de las prácticas individuales y colectivas de mujeres y hombres, en contextos históricos y espaciales específicos. La narcocultura sería entonces el sistema semiótico producido en torno al negocio transnacional de tráfico ilegal de drogas, tal como se vive en la frontera norte de México. La narcocultura, tal como se define en este trabajo es un sistema semiótico con límites difusos. Así, las distinciones entre el mundo ilegal del narcotráfico y el mundo de la legalidad externo a este negocio, en el mejor de los casos son borrosas, en el peor, ficticias. La narcocultura trasciende límites territoriales, es un fenómeno cultural transnacional.
Fue necesario delinear las características de los estudios culturales latinoamericanos y los Kulturwissenschaften en Alemania, para distinguir las genealogías de estas dos diferentes perspectivas, entender sus diferencias, pero, sobre todo, encontrar los puntos en común entre ellas. La coincidencia central fue el carácter transdisciplinario de estas dos tradiciones académicas. Los estudios culturales entonces se entienden como un espacio de articulación entre disciplinas (Castro Gómez, 2002), que no tiene como objetivo la unificación sino la pluralización de significados, actitudes y modos de percepción (Bachmann-Medick, 2016). La transdisciplina permite trazar las complejidades de los fenómenos culturales, creando puentes entre diferentes formas de conocimiento y prácticas de investigación.
El feminismo interseccional es una perspectiva central en el trabajo de investigación. Una contribución del feminismo a los estudios culturales que influye en esta investigación es cuestionar “Hombre” y “Mujer” como esencias naturales dadas e inmutables, desde la premisa que “los signos "hombre" y "mujer" son construcciones discursivas que el lenguaje de la cultura proyecta e inscribe en el escenario de los cuerpos, disfrazando sus montajes de signos tras la falsa apariencia de que lo masculino y lo femenino son verdades naturales, ahistóricas” (Richard, 2009, p. 77). Los estudios culturales feministas suponen que estos signos se construyen en un sistema de representaciones que articulan subjetividades en mundos culturales concretos. Su objetivo entonces es develar en las prácticas significantes, los elementos ideológicos que configuran los signos y los conflictos que se suscitan a través del uso e interpretación de éstos.
Estos signos adquieren múltiples significados y lecturas de acuerdo con especificidades que se distinguen en la diferencia. La interseccionalidad, dentro del feminismo es un discurso teórico y metodológico que aboga por reconocer que el signo “mujer” no es una categoría absoluta, y por lo tanto no puede explicar por sí misma las variadas experiencias vitales de las mujeres. Las diferencias se vuelven legibles cuando se ponen en juego con otras categorías sociales como la posición social, la raza, la edad y la discapacidad. Las diferencias sociales están fincadas en diferentes discursos que naturalizan los diferentes atributos de estas categorías sociales cuando, para esta perspectiva, son socialmente construidos y cambiantes. El objetivo de una perspectiva interseccional es identificar cómo interactúan diferentes categorías sociales en instituciones, prácticas y subjetividades, para entender cómo se materializan las desigualdades a través del tiempo.
Los conceptos teóricos que guían esta tesis son cuerpo y subjetividad. Para esta tesis, el cuerpo se entiende como un sitio de articulación, donde se materializan códigos culturales y el orden social. El cuerpo puede entenderse como una frontera dinámica y mutable, donde convergen lo físico, lo simbólico y lo social. Sujeto y cuerpo son mutuamente constitutivos; el cuerpo es el medio a través del cual el sujeto vive experiencias en el mundo social, y son esas experiencias las que llevan al sujeto a encarnar las diferencias sociales, materializadas en género, sexo, clase social y raza.
A pesar de esta relación indisociable, para facilitar el análisis, una parte se concentra en el cuerpo y otra en la subjetividad. Así, para entender la dimensión corporal se puso en tensión la representación con la experiencia vivida, a través del análisis audiovisual y la observación etnográfica leída en conjunto. En el caso de la subjetividad, se puso en tensión la vida en la narrativa de ficción con las narraciones de vida en entrevistas, para también encontrar los puentes entre las representaciones y la experiencia vital.
Esta investigación fue un estudio cualitativo y transdisciplinario. Se utilizaron diversos recursos metodológicos para construir el análisis. Se realizó observación etnográfica en diversos bares y clubs a ambos lados de la frontera, que son frecuentados por personas que se adscriben al mundo de la narcocultura o bien, que trabajan dentro de las redes del narcotráfico. En las incursiones a estos sitios, se observó el físico de las mujeres: su manera de vestir, su arreglo personal, sus formas corporales. Se observó la conducta: las gestualidades y las interacciones con otros sujetos en el espacio. Además, se observó el espacio, para ver cómo se establecían reglas, límites y jerarquizaciones en la disposición física de los lugares visitados. Se analizaron tres videos de narcocorridos a través de la video hermenéutica, para determinar cómo se representan las mujeres en estos artefactos culturales, usando los mismos criterios físicos y conductuales que mencioné anteriormente.
El análisis de los videos de la mano del trabajo etnográfico ayudó a profundizar en los significados atribuidos a la corporalidad femenina, y también a los impactos que estos significados tienen en las vivencias y relaciones de estas mujeres.
Se realizaron 5 entrevistas semi estructuradas con mujeres que se identificaban con la narcocultura. Algunas sólo simpatizan con el estilo de vida, otras estuvieron involucradas de alguna manera en el negocio ilegal de drogas. En las entrevistas se exploraron narraciones sobre sus vidas donde se revelaban discursos sobre qué es lo femenino, qué significa ser mujer y cómo se vive el ser mujer en el mundo del narcotráfico. Adicionalmente, utilicé las narraciones de dos textos literarios de la narrativa sobre narcotráfico del norte de México. En estos dos textos, los personajes principales son mujeres. Analicé cómo se construye al sujeto femenino en la narración y qué discursos se transparentan en el texto sobre la feminidad y ser una mujer en el mundo del narco.
Aquí también se puso en tensión la representación y la experiencia de vida, buscando en el análisis de la narración literaria y las experiencias narradas por las mujeres, discursos comunes que explicaran los procesos de subjetivación femenina dentro de la narcocultura mexicana.
La primera parte del análisis articuló la observación etnográfica con el material audiovisual para entender las exigencias estéticas que la narcocultura demanda a las mujeres y las maneras en que ellas transforman su cuerpo para complacer esta demanda.
La narcocultura impone a las mujeres un ideal estético que se convierte en un medio de acceso a un tipo de poder. Este ideal exige un tipo particular de fisonomía y de apariencia personal, que las mujeres intentan reproducir a través de intervenciones en el cuerpo, con el maquillaje y el peinado y/o la cirugía estética. Además, demanda cierto estilo de moda, en ropa y accesorios, de marcas de lujo de consumo global. Entre más fielmente se reproduzca este ideal, las mujeres están en posibilidad de acceder a beneficios económicos y sociales que les dan márgenes de acción dentro de este entorno social. El cuerpo de las mujeres se convierte en el recurso primario para la movilidad social y la agencia dentro de este mundo. El cuerpo es el signo principal para determinar el lugar de las mujeres dentro de los sistemas de jerarquización, de inclusión y exclusión en los espacios físicos y sociales que fabrica el narcotráfico. Estos mecanismos de diferencia reproducen las desigualdades sociales, de género, edad, posición social y raza que se observan en otros ámbitos de la sociedad mexicana.
La observación etnográfica y el análisis audiovisual revelan que las posibilidades para performar la feminidad está confinado a limites muy estrechos. Alicia Gaspar de Alba llama a esto The Three Maria Syndrome, que ella define como “the patriarchal social discourse of Chicano/Mexicano culture that constructs women’s gender and sexuality according to three Biblical archetypes -virgins, mothers and whores-” (Gaspar de Alba, 2014, pos.3412). Estas representaciones femeninas son alegorías a las constricciones que la cultura machista mexicana impone sobre las mujeres, sometiéndolas a un repertorio restringido de opciones de vida y al control social de su sexualidad. Las mujeres dentro de la narcocultura tienen un lugar en él en función de su belleza física, el cuerpo es el referente principal para definirse como sujetos.
Las mujeres son objetos de deseo, cuya belleza es una joya más para la corona de un narcotraficante, una posesión más para ostentar su poderío. Al mismo tiempo, aparecen cada vez más las representaciones femeninas como sujetos activos, participando del negocio y de la violencia a la par de los hombres. Se observan transgresiones al ideal de feminidad que se exige a la mujer tradicional en la cultura mexicana. La docilidad, la suavidad y la sumisión que se espera, el recato y la compostura, no está presente. Las mujeres adoptan cualidades consideradas masculinas, tomando para sí el ejercicio de la violencia y la agresividad sexual para demostrar que ellas también pueden navegar un mundo agresivo e hipermasculino. A pesar de esto, esta mujer guerrera y valiente está dentro de los confines limitados que la cultura patriarcal impone al régimen heterosexual. Siguen al pie de la letra la prescripción del Three Maria Syndrome.
Esto queda patente un sistema de jerarquización a través de la cual se evalúa a las mujeres dentro de la narcocultura. Las mujeres son juzgadas a partir de criterios que intersectan componentes raciales, de género y de clase. Aunque las maneras en las que estas marcas de diferencia se encarnan en un cuerpo femenino de manera muy diversa, se puede identificar, a través de las representaciones y la observación etnográfica, que las mujeres más privilegiadas, son mujeres que encarnan los signos de una posición económica alta: tienen tez clara, son atractivas y cuidan su apariencia para presentar signos de feminidad de manera discreta, y su conducta proyecta compostura y respetabilidad, en función de su restricción, particularmente en la expresión de la sexualidad. A las mujeres que encarnan estos signos de feminidad se les respeta y se consideran valiosas. Su valor se formaliza a través de la respetabilidad del contrato matrimonial: este tipo de performance de género lo reproducen, por lo general, mujeres esposas de narcotraficantes. En el otro extremo del espectro están las mujeres menos valoradas: son mujeres morenas, que utilizan una estética asociada con la clase trabajadora, por lo general ostentosa y recargada de decoraciones. La conducta de estas mujeres se juzga como vulgar y sin restricciones. A las mujeres que encarnan este tipo de feminidad se les discrimina y cosifica, son las más vulnerables a la violencia en función del poco valor que tienen dentro del mundo del narcotráfico.
La buchona representa una versión devaluada de la feminidad, que choca con el decoro y la discreción que exigen las normas tradicionales de género. Son mujeres que se consideran vulgares, porque sus cuerpos portan signos de una sexualidad agresiva, porque adoptan conductas que irrumpen las restricciones sociales impuestas a las mujeres, porque sus prácticas y consumos culturales están asociadas a las clases trabajadoras y rurales. En las mujeres que entrevisté hay un conflicto entre la atractiva libertad que promete la transgresión de ser buchona y el deseo de respetabilidad que otorga ser una mujer que cumple con lo que la sociedad exige. Uno de los dilemas al centro de performar el cuerpo buchón es la batalla entre una feminidad aceptada socialmente, pero restrictiva y una feminidad que otorga poder, pero castiga.
Por este motivo, las mujeres que entrevisté rechazaban ser nombradas como buchonas y preferían llamarse a sí mismas cabronas. En este contexto particular, la palabra cabrona es una resignificación de un término coloquial castellano, usado para ofender. Aquí, la mujer cabrona se convierte en un eje articulador para la constitución de subjetividades femeninas dentro de la narcocultura. La cabrona es un tropo femenino que entrelaza narrativas sobre ser mujer que circulan a nivel global con narrativas locales sobre la feminidad. Asumirse “cabrona”, se convierte en un recurso para enfrentar un mundo violento y encontrar estrategias de acción en un espacio claramente dominado por los hombres.
La cabrona representa independencia y fuerza, autonomía y acción. La cabrona confronta los discursos tradicionales de una feminidad abnegada y dócil, con diferentes matices, aparentemente interpelando la dominación masculina. Por lo mismo, carga un fuerte estigma. La cultura de masas también produce representaciones sobre la cabrona. Se transmiten en discursos de género que circulan a través de imágenes en las redes sociales, en libros y workshops del mercado de autoayuda en el mundo entero, y que promueven una idea de mujer indócil frente a la gente de su entorno, suscrita al consumo y al individualismo de la cultura capitalista. En estas representaciones culturales contemporáneas, la mujer es fuerte e insumisa, pero conservando códigos corporales y prácticas femeninas.
En el contexto concreto de la narcocultura, los discursos globales sobre una mujer fuerte e independiente con poder económico y a cargo de su sexualidad, se encuentran con las condiciones particulares del norte mexicano. La violencia extrema, el machismo, las desigualdades sociales pronunciadas y la crisis de legitimidad del Estado intervienen para que estos discursos globales sobre la mujer muten en la representación de la buchona y la cabrona, interpretaciones locales de un discurso de género global. Para las mujeres, asumirse cabrona es un recurso para enfrentar un mundo violento y encontrar estrategias de acción en un espacio claramente dominado por los hombres. Ayuda a enfrentar la violencia perpetrada sobre ella, abre la posibilidad a ser la victimaria. La cabrona es la reacción que provoca el cuerpo femenino vulnerable y vulnerado, pero también, es la posibilidad de apropiarse de la violencia para ejercerla sobre otros cuerpos. Implica independencia, libertad sexual y éxito económico, evidenciadas por el consumo y el estilo de vida. Cuando niegan ser buchonas, están rechazando todos los estigmas que acarrea la palabra. No se reconocen en la discriminación de clase, las connotaciones raciales y los prejuicios sexistas que contiene. Prefieren cabrona porque es una manera de escindirse de los discursos negativos que se vuelcan sobre ellas, es un camino de acceso a una feminidad global que los medios de comunicación masiva presentan como ideal.
El análisis exploró qué elementos componían este tropo femenino a través de las entrevistas a mujeres y de personajes femeninos en novelas sobre narcotráfico, para encontrar puentes entre la ficción y la experiencia vital. La belleza y la capacidad de seducir tiene una utilidad ambivalente. Por un lado, todo el tiempo, dinero y cuidado que se invierte en apropiarse de un ideal estético, es para convertirse en una mujer que un narco pueda presumir. Para las mujeres es un motivo de orgullo saberse deseadas y puestas en aparador. Las mujeres están sometidas a las presiones que genera la creencia de que, para sobrevivir, hay que ser bella. En los textos literarios y en las entrevistas, se transparenta una naturalización del lugar de la mujer como objeto de ostentación para el hombre y, además, la validación que sienten las mujeres al ser reconocidas como bellas. La ficción y la vida nos presentan la precaria condición del sujeto femenino en la narcocultura. Es una subjetividad anclada a los discursos que demandan un ideal de belleza imposible para las mujeres y que encajonan el ser mujer a los caprichos y necesidades del hombre.
Sin embargo, la belleza femenina tiene otra faceta. La subjetividad femenina en la narcocultura no sólo es resultado del sometimiento de la mujer a los discursos que regulan su apariencia y su conducta. La belleza también es un instrumento al servicio de las mujeres para acceder a dinero y poder. La belleza y el poder de seducción femenino se convierten en estrategias de subsistencia, y esto transforma a la mujer de un objeto sometido a un sujeto que somete. La belleza y la seducción podrán dar a las mujeres ciertos márgenes de acción, pero esto tiene límites muy claros. Aunque estas estrategias femeninas muevan la balanza de poder hacía el sujeto femenino, hay que recordar el contexto. Están insertas en un mundo violento y machista, así que ejercer ese poder es un ejercicio de equilibrio muy delicado y arriesgado. Las mujeres que habitan la narcocultura están inmersas es un mundo de violencia, y no conocer y respetar las reglas y límites significa un riesgo de muerte. La muerte violenta es una consecuencia muy real por cometer errores en este mundo.
Esto lleva a tercer componente de ser cabrona: el riesgo. Para los hombres y mujeres que se involucran en el mundo cultural del narcotráfico, perseguir el riesgo es parte integral de vivir y es una parte importante de la constitución de subjetividades en la narcocultura. En las narraciones de las entrevistas y en las narraciones literarias, hay muchos momentos donde las mujeres viven situaciones de riesgo que ponen en peligro hasta sus vidas. A través de las narraciones se asoma la manera en qué ellas interpretan su papel en la situación y cómo se ven a sí mismas en función de esas experiencias. El riesgo le da sentido al carácter recio y atrevido que demanda asumir el rol de una cabrona, pero también expone la vulnerabilidad de la condición de las mujeres en un mundo violento. Tomar riesgos es otra manera de afirmarse como mujeres fuertes y poner distancia con las disposiciones de género que les exigen ser dóciles y pasivas. Tienen que demostrar lo que valen frente a un mundo dominado por hombres y el control de sus emociones juega un rol fundamental en lograr esto. Sin embargo, el reconocimiento del miedo y vulnerabilidad es, paradójicamente, lo que las ayuda a sobrevivir.
Detrás de los discursos de fuerza y poder femenino, se revela la fragilidad de unas vidas sumergidas en un mundo donde la violencia y el machismo deja a las mujeres en el filo de la vida y de la muerte. Para el caso que nos compete, el vacío institucional para garantizar seguridad a las mujeres en México deja a estas mujeres absolutamente expuestas, y cobra sentido la adopción del discurso de la cabrona como estrategia de persistencia. Al investirse como cabronas, encuentran una manera de enfrentarse al mundo violento al que deciden pertenecer, aunque al final de cuentas, permanecen atrapadas en él.
Anhand einer inhaltlichen Untersuchung der französischen fünfbändigen Oktavausgabe seines Essai politique sur le royaume de la Nouvelle-Espagne (1811), unter besonderer Berücksichtigung der intertextuellen Bezüge, wird Alexander von Humboldt auf multiplen Ebenen als Denker zwischen Europa und Amerika ausgewiesen. In seinem Werk über Neuspanien durchbricht er die Inferiorisierung amerikanischer bzw. kreolischer Wissenschaftler und schafft ein Bewusstsein fernab eurozentrischer Denkmuster. Dies äußert sich unter anderem in Humboldts unvoreingenommener intertextueller Einbeziehung von Vertretern verschiedener Strömungen der Aufklärung, insbesondere des kreolischen aufklärerischen Denkens.
Delay
(2018)
Das Sinnbild »Diabolisches Spiel mit den Zeitmaschinen« spiegelt eine Sicht auf den Musikeffekt »Delay« und seine wechselseitige Beziehung zwischen Technik, Musikproduktion und Rezeption wider. Der durch die beabsichtigte Verzögerung eines akustischen Signals erzeugte und häufig als »Echo« beschriebene Effekt kann nicht nur als echoähnliche Verzögerung, sondern auch in anderen Weisen eingesetzt und vernommen werden. Dies zeigt die Dub-Musik, in der das Delay von der ersten Stunde bis in seine gegenwärtige Ausprägung zum Stilmerkmal wurde. Lee »Scratch« Perry ist Zeitzeuge und Exponent dieser Entwicklung. Sein Schaffen bildet den geeigneten Anlass, den Zeitgeist des Delay und seine Wahrnehmung als psychoakustischen Effekt zu erforschen. Damit führt dieses Buch von einer allgemeinen Beschreibung und Neuverortung des Delays in den prominenten Verwendungskontext der Dub-Musik und die Erkundung eines vielschichtigen Bezugskosmos aus Natur, Technik, Religion, Okkultismus und (Musik-)Kultur.
Synchrotron-based angle-resolved time-of-flight electron spectroscopy for dynamics in dichalogenides
(2018)
Der Anspruch der Biologie, Leben zum Hauptgegenstand zu haben, provoziert Fragen in Anbetracht von Methoden wie der Mikroskopie. Die vorliegende Bild- und Medientheorie der Mikroskopie rekonstruiert und reflektiert biologische Praktiken der Licht- und Elektronenmikroskopie.Dabei geht sie systematisch von der Auswahl der Objekte über die Präparation und Beobachtung bis hin zur Aufzeichnung des Sichtbargemachten in Form von Zeichnung, Fotografie oder Datenbild unter Einbeziehung von historischem Material vor. Die umfassende Untersuchung des Bildgebungsprozesses, seiner medialen Bedingungen sowie technischen und methodologischen Grundlagen zeigt, dass die mikroskopische Beobachtung kein passiver oder rein rezeptiver Vorgang, sondern von Beginn an in die Darstellung des Beobachteten involviert ist – bis zu einem Grad, in dem sich Beobachtung als schädigender Eingriff erweisen kann. Das Buch wirft somit zugleich epistemologische wie wissenschaftstheoretische Fragen auf.
Samarium hexaboride
(2018)
Im historischen Zentrum der mittelalterlichen Stadt Capua hat sich mit den drei Kirchen S. Salvatore „Maggiore“ a Corte, S. Giovanni a Corte und S. Michele a Corte eine Gruppe von Sakralbauten erhalten, die nicht nur durch ihre übereinstimmende namentliche Attribution einen Zusammenhang mit dem langobardischen Fürstenhof der Stadt offenbaren, sondern auch durch die räumliche Disposition im urbanistischen Gefüge. Im vorliegenden Buch wird die überkommene Bausubstanz einer grundlegenden Analyse unterzogen, um herauszuarbeiten, welche Bestandteile den ältesten Bauphasen zuzuordnen sind und somit als langobardenzeitlich angesprochen werden können. Eine ausführliche Untersuchung der zugehörigen Bauplastik ergänzt gleichwertig diesen ersten Teil. Die Kontextualisierung der Ergebnisse hilft dabei, ein Bild von der Kunst und Architektur des in Süditalien an Monumenten eher armen 10. Jahrhunderts zu generieren und erlaubt Rückschlüsse auf den geistigen Hintergrund, vor dem die drei Hofkirchen entstanden sind.
Suchmaschinen spielen eine überragend wichtige Rolle für den Informationszugang im Internet und damit für die individuelle und kollektive Meinungsbildung. Gleichzeitig wird der Suchmaschinenmarkt nahezu vollständig von einem einzigen Anbieter beherrscht – Google. Angesichts dessen wird vermehrt eine Regulierung von Suchmaschinen zur Sicherung der für die Demokratie unabdingbaren Meinungsvielfalt gefordert. Die Untersuchung geht der Gebotenheit und den Grenzen einer solchen Regulierung nach und stellt die Frage nach einem kommunikationsverfassungsrechtlichen Schutz von und vor Suchmaschinen.
Anne-Katrin Wolf beschäftigt sich mit der Aktivlegitimation im Individualbeschwerdeverfahren der UN-Menschenrechtskonventionen. Sie gibt einerseits eine leitfadenartige Übersicht zum Zulässigkeitskriterium der Aktivlegitimation. Andererseits zeigt sie, dass die Auslegungspraxis der UN-Ausschüsse zu dessen Voraussetzungen derzeit an einigen Stellen zu eng gefasst ist, um einen effektiven Menschenrechtsschutz zu gewährleisten. Im Zentrum steht dabei die Kategorisierung der UN-Menschenrechtskonventionen anhand der jeweiligen Regelungsmaterie und die daran anknüpfende, unterschiedlich weit reichenden Beschwerdemöglichkeiten von Individuen und Kollektiven wie Verbänden oder Nichtregierungsorganisationen. Sofern eine Ausgestaltung durch die Ausschüsse selbst noch nicht erfolgt ist oder die Autorin bisher angewendeten Kriterien als defizitär bewertet, entwickelt sie Vorschläge zu einer möglichen Ausformung des Kriteriums der Aktivlegitimation in der Zusammenschau mit dem jeweiligen Schutzgehalt der Konvention.
On a small scale
(2018)
This study argues that micro relations matter in peacekeeping. Asking what makes the implementation of peacekeeping interventions complex and how complexity is resolved, I find that formal, contractual mechanisms only rarely effectively reduce complexity – and that micro relations fill this gap. Micro relations are personal relationships resulting from frequent face-to-face interaction in professional and – equally importantly – social contexts.
This study offers an explanation as to why micro relations are important for coping with complexity, in the form of a causal mechanism. For this purpose, I bring together theoretical and empirical knowledge: I draw upon the current debate on ‘institutional complexity’ (Greenwood et al. 2011) in organizational institutionalism as well as original empirical evidence from a within-case study of the peacekeeping intervention in Haiti, gained in ten weeks of field research. In this study, scholarship on institutional complexity serves to identify theoretical causal channels which guide empirical analysis. An additional, secondary aim is pursued with this mechanism-centered approach: testing the utility of Beach and Pedersen’s (2013) theory-testing process tracing.
Regarding the first research question – what makes the implementation of peacekeeping interventions complex –, the central finding is that complexity manifests itself in the dual role of organizations as cooperation partners and competitors for (scarce) resources, turf and influence. UN organizations, donor agencies and international NGOs implementing peacekeeping activities in post-conflict environments have chronic difficulty mastering both roles because they entail contradictory demands: effective cooperation requires information exchange, resource and responsibility-sharing as well as external scrutiny, whereas prevailing over competitors demands that organizations conceal information, guard resources, increase relative turf and influence, as well as shield themselves from scrutiny. Competition fuels organizational distrust and friction – and impedes cooperation.
How is this complexity resolved? The answer to this second research question is that deep-seated organizational competition is routinely mediated – and cooperation motivated – in micro relations and micro interaction. Regular, frequent face-to-face interaction between individual organizational members generates social resources that help to transcend organizational distrust and conflict, most importantly familiarity with each other, personal trust and belief in reciprocity. Furthermore, informal conflict mediation and control mechanisms – namely, open discussion, mutual monitoring in direct interaction and social exclusion – enhance solidarity and mutual support.
Nanoparticles (NPs) are particles between 1 and 100 nanometers in size. They have attracted enormous research interests owing to their remarkable physicochemical properties and potential applications in the optics, catalysis, sensing, electronics, or optical devices. The thesis investigates systems of NPs attached to planar substrates.
In the first part of the results section of the thesis a new method is presented to immobilize NPs. In many NP applications a strong, persistent adhesion to substrates is a key requirement. Up to now this has been achieved with various methods, which are not always the optimum regarding adhesion strength or applicability. We propose a new method which uses capillarity to enhance the binding agents in the contact area between NP and substrate. The adhesion strength resulting from the new approach is investigated in detail and it is shown that the new approach is superior to older methods in several ways.
The following section presents the optical visualization of nano-sized objects through a combination of thin film surface distortion and interference enhanced optical reflection microscopy. It is a new, fast and non-destructive technique. It not only reveals the location of NPs as small as 20nm attached to planar surfaces and embedded in a molecularly thin liquid film. It also allows the measurement of the geometry of the surface distortion of the liquid film. Even for small NPs the meniscus reaches out for micrometers, which is the reason why the NPs produce such a pronounced optical footprint.
The nucleation and growth of individual bubbles is presented in chapter 5. Nucleation is a ubiquitous natural phenomenon and of great importance in numerous industrial processes. Typically it occurs on very small scales (nanometers) and it is of a random nature (thermodynamics of small systems). Up to now most experimental nucleation studies deal with a large number of individual nucleation processes to cope with its inherently statistical, spatio-temporal character. In contrast, in this thesis the individual O2-bubble formation from single localized platinum NP active site is studied experimentally. The bubble formation is initiated by the catalytic reaction of H2O2 on the Pt surface. It is studied how the bubble nucleation and growth depends on the NP size, the H2O2 concentration and the substrate surface properties. It is observed that in some cases the bubbles move laterally over the substrate surface, driven by the O2-production and the film ablation.
Neuroinflammatory and neurodegenerative diseases such as Parkinson's (PD) and multiple sclerosis (MS) often result in a severe impairment of the patient´s quality of life. Effective therapies for the treatment are currently not available, which results in a high socio-economic burden. Due to the heterogeneity of the disease subtypes, stratification is particularly difficult in the early phase of the disease and is mainly based on clinical parameters such as neurophysiological tests and central nervous imaging. Due to good accessibility and stability, blood and cerebrospinal fluid metabolite markers could serve as surrogates for neurodegenerative processes. This can lead to an improved mechanistic understanding of these diseases and further be used as "treatment response" biomarkers in preclinical and clinical development programs. Therefore, plasma and CSF metabolite profiles will be identified that allow differentiation of PD from healthy controls, association of PD with dementia (PDD) and differentiation of PD subtypes such as akinetic rigid and tremor dominant PD patients. In addition, plasma metabolites for the diagnosis of primary progressive MS (PPMS) should be investigated and tested for their specificity to relapsing-remitting MS (RRMS) and their development during PPMS progression.
By applying untargeted high-resolution metabolomics of PD patient samples and in using random forest and partial least square machine learning algorithms, this study identified 20 plasma metabolites and 14 CSF metabolite biomarkers. These differentiate against healthy individuals with an AUC of 0.8 and 0.9 in PD, respectively. We also identify ten PDD specific serum metabolites, which differentiate against healthy individuals and PD patients without dementia with an AUC of 1.0, respectively. Furthermore, 23 akinetic-rigid specific plasma markers were identified, which differentiate against tremor-dominant PD patients with an AUC of 0.94 and against healthy individuals with an AUC of 0.98. These findings also suggest more severe disease pathology in the akinetic-rigid PD than in tremor dominant PD. In the analysis of MS patient samples a partial least square analysis yielded predictive models for the classification of PPMS and resulted in 20 PPMS specific metabolites. In another MS study unknown changes in human metabolism were identified after administration of the multiple sclerosis drug dimethylfumarate, which is used for the treatment of RRMS. These results allow to describe and understand the hitherto completely unknown mechanism of action of this new drug and to use these findings for the further development of new drugs and targets against RRMS.
In conclusion, these results have the potential for improved diagnosis of these diseases and improvement of mechanistic understandings, as multiple deregulated pathways were identified. Moreover, novel Dimethylfumarate targets can be used to aid drug development and treatment efficiency. Overall, metabolite profiling in combination with machine learning identified as a promising approach for biomarker discovery and mode of action elucidation.
Der 20. Juli 1944 zählt zu den Schlüsselereignissen der deutschen Geschichte des 20. Jahrhunderts. Das missglückte Attentat von Claus Schenk Graf von Stauffenberg auf Adolf Hitler und der anschließende Umsturzversuch sind zum Symbol des Widerstandes gegen den Nationalsozialismus geworden. Von den Ereignissen völlig überrascht, hatte das NS-Regime in Bezug auf die Gruppe der Verschwörer sofort festgelegt, dass in der Öffentlichkeit nur von einer »ganz kleinen Clique« die Rede sein dürfe – eine Formulierung, die mitunter noch heute das Bild des Widerstandskreises prägt.
Die vorliegende Analyse zeigt erstmals anhand von zahlreichen Netzwerkvisualisierungen, was die NS-Ermittler tatsächlich über das große und komplexe zivile und militärische Netzwerk vom 20. Juli 1944 wussten, das so unterschiedliche gesellschaftliche Gruppen umfasste wie Offiziere, Verwaltungsbeamte, Diplomaten, Juristen, Industrielle, Theologen, Gutsbesitzer, Gewerkschafter und Sozialdemokraten. Zeitgenössische Briefe und Tagebücher verdeutlichen schließlich das geschickte Agieren der Verschwörer vor und nach dem Umsturzversuch und offenbaren zudem die Fehlerhaftigkeit der NS-Quellen.
Die Frage nach dem Zusammenhalt einer ganzen Gesellschaft ist eine der zentralen Fragen der Sozialwissenschaften und Soziologie. Seit dem Übergang in die Moderne bildet das Problem des Zusammenhalts von sich differenzierenden Gesellschaften den Gegenstand des wissenschaftlichen und gesellschaftlichen Diskurses. In der vorliegenden Studie stellt soziale Integration eine Form der gelungenen Vergesellschaftung dar, die sich in der Reproduktion von symbolischen und nicht-symbolischen Ressourcen artikuliert. Das Resultat dieser Reproduktion sind pluralistische Vergesellschaftungen, die, bezogen auf politische Präferenzen, konfligierende Interessen verursachen. Diese Präferenzen kommen in unterschiedlichen Formen, in ihrer Intensität und Wahrnehmung der politischen Partizipation zum Ausdruck. Da moderne politische Herrschaft aufgrund der rechtlichen und institutionellen Ausstattung einen bedeutsamen Einfluss auf soziale Reproduktion ausüben kann (z.B. durch Sozialpolitik), stellt direkte Beeinflussung politischer Entscheidungen, als Artikulation von sich aus den Konfliktlinien etablierenden, unterschiedlichen Präferenzen, das einzige legitime Mittel zwecks Umverteilung von Ressourcen auf der Ebene des Politischen dar. Somit wird die Konnotation zwischen Integration und politischer Partizipation sichtbar. In die Gesellschaft gut integrierte Mitglieder sind aufgrund einer breiten Teilnahme an Reproduktionsprozessen in der Lage, eigene Interessen zu erkennen und durch politische Aktivitäten zum Ausdruck zu bringen. Die empirischen Befunde scheinen den Eindruck zu vermitteln, dass der demokratische Konflikt in der modernen Gesellschaft nicht mehr direkt von Klassenzugehörigkeit und Klasseninteressen geprägt wird, sondern durch den Zugang zu und die Verfügbarkeit von symbolischen und nicht-symbolischen Ressourcen geformt wird. In der Konsequenz lautet die Fragestellung der vorliegenden Arbeit, ob integrierte Gesellschaften politisch aktiver sind.
Die Fragestellung der Arbeit wird mithilfe von Aggregatdaten demokratisch-verfasster politischer Systemen untersucht, die als etablierte Demokratien gelten und unterschiedlich Breite wohlfahrtstaatlichen Maßnahmen aufweisen. Die empirische Überprüfung der Hypothesen erfolgte mithilfe von bivariaten und multivariaten Regressionsanalysen. Die überprüften Hypothesen lassen sich folgend in einer Hypothese zusammenfassen: Je stärker die soziale Integration einer Gesellschaft, desto größer ist die konventionelle bzw. unkonventionelle politische Partizipation. Verallgemeinert ist die Aussage zulässig, dass soziale Integration einer Gesellschaft positive Effekte auf die Häufigkeit politischer Partizipation innerhalb dieser Gesellschaft hat. Stärker integrierte Gesellschaften sind politisch aktiver und dies unabhängig von der Form (konventionelle oder unkonventionelle) politischer Beteiligung. Dabei ist der direkte Effekt der gesamtgesellschaftlichen Integration auf die konventionellen Formen stärker als auf unkonventionellen. Diese Aussage ist nur zulässig, wenn die Elemente des Wahlsystems, wie z.B. Verhältniswahlrecht, und das BIP nicht berücksichtigt werden. Auf der Grundlage der Ergebnisse mit Kontrollvariablen erlauben die Daten die auf die Makroebene bezogene Aussage, dass neben einem hohen Niveau sozialer Integration auch ein durch (Mit-)Beteiligung bestimmtes Wahlsystem und ein hoher wirtschaftlicher Entwicklungsgrad begünstigend für ein hohes Niveau politischer Partizipation sind.
Reversible-deactivation radical polymerization (RDRP) is without any doubt one of the most prevalent and powerful strategies for polymer synthesis, by which well-defined living polymers with targeted molecular weight (MW), low molar dispersity (Ɖ) and diverse morphologies can be prepared in a controlled fashion. Atom transfer radical polymerization (ATRP) as one of the most extensive studied types of RDRP has been particularly emphasized due to the high accessibility to hybrid materials, multifunctional copolymers and diverse end group functionalities via commercially available precursors. However, due to catalyst-induced side reactions and chain-chain coupling termination in bulk environment, synthesis of high MW polymers with uniform chain length (low Ɖ) and highly-preserved chain-end fidelity is usually challenging. Besides, owing to the inherited radical nature, the control of microstructure, namely tacticity control, is another laborious task. Considering the applied catalysts, the utilization of large amounts of non-reusable transition metal ions which lead to cumbersome purification process, product contamination and complicated reaction procedures all delimit the scope ATRP techniques.
Metal-organic frameworks (MOFs) are an emerging type of porous materials combing the properties of both organic polymers and inorganic crystals, characterized with well-defined crystalline framework, high specific surface area, tunable porous structure and versatile nanochannel functionalities. These promising properties of MOFs have thoroughly revolutionized academic research and applications in tremendous aspects, including gas processing, sensing, photoluminescence, catalysis and compartmentalized polymerization. Through functionalization, the microenvironment of MOF nanochannel can be precisely devised and tailored with specified functional groups for individual host-guest interactions. Furthermore, properties of high transition metal density, accessible catalytic sites and crystalline particles all indicate MOFs as prominent heterogeneous catalysts which open a new avenue towards unprecedented catalytic performance. Although beneficial properties in catalysis, high agglomeration and poor dispersibility restrain the potential catalytic capacity to certain degree.
Due to thriving development of MOF sciences, fundamental polymer science is undergoing a significant transformation, and the advanced polymerization strategy can eventually refine the intrinsic drawbacks of MOF solids reversely. Therefore, in the present thesis, a combination of low-dimensional polymers with crystalline MOFs is demonstrated as a robust and comprehensive approach to gain the bilateral advantages from polymers (flexibility, dispersibility) and MOFs (stability, crystallinity). The utilization of MOFs for in-situ polymerizations and catalytic purposes can be realized to synthesize intriguing polymers in a facile and universal process to expand the applicability of conventional ATRP methodology. On the other hand, through the formation of MOF/polymer composites by surface functionalization, the MOF particles with environment-adjustable dispersibility and high catalytic property can be as-prepared.
In the present thesis, an approach via combination of confined porous textures from MOFs and controlled radical polymerization is proposed to advance synthetic polymer chemistry. Zn2(bdc)2(dabco) (Znbdc) and the initiator-functionalized Zn MOFs, ZnBrbdc, are utilized as a reaction environment for in-situ polymerization of various size-dependent methacrylate monomers (i.e. methyl, ethyl, benzyl and isobornyl methacrylate) through (surface-initiated) activators regenerated by electron transfer (ARGET/SI-ARGET) ATRP, resulting in polymers with control over dispersity, end functionalities and tacticity with respect to distinct molecular size. While the functionalized MOFs are applied, due to the strengthened compartmentalization effect, the accommodated polymers with molecular weight up to 392,000 can be achieved. Moreover, a significant improvement in end-group fidelity and stereocontrol can be observed. The results highlight a combination of MOFs and ATRP is a promising and universal methodology to synthesize versatile well-defined polymers with high molecular weight, increment in isotactic trial and the preserved chain-end functionality.
More than being a host only, MOFs can act as heterogeneous catalysts for metal-catalyzed polymerizations. A Cu(II)-based MOF, Cu2(bdc)2(dabco), is demonstrated as a heterogeneous, universal catalyst for both thermal or visible light-triggered ARGET ATRP with expanded monomer range. The accessible catalytic metal sites enable the Cu(II) MOF to polymerize various monomers, including benzyl methacrylate (BzMA), styrene, methyl methacrylate (MMA), 2-(dimethylamino)ethyl methacrylate (DMAEMA) in the fashion of ARGET ATRP. Furthermore, due to the robust frameworks, surpassing the conventional homogeneous catalyst, the Cu(II) MOF can tolerate strongly coordinating monomers and polymerize challenging monomers (i.e. 4-vinyl pyridine, 2-vinyl pyridine and isoprene), in a well-controlled fashion. Therefore, a synthetic procedure can be significantly simplified, and catalyst-resulted chelation can be avoided as well. Like other heterogeneous catalysts, the Cu(II) MOF catalytic complexes can be easily collected by centrifugation and recycled for an arbitrary amount of times.
The Cu(II) MOF, composed of photostimulable metal sites, is further used to catalyze controlled photopolymerization under visible light and requires no external photoinitiator, dye sensitizer or ligand. A simple light trigger allows the photoreduction of Cu(II) to the active Cu(I) state, enabling controlled polymerization in the form of ARGET ATRP. More than polymerization application, the synergic effect between MOF frameworks and incorporated nucleophilic monomers/molecules is also observed, where the formation of associating complexes is able to adjust the photochemical and electrochemical properties of the Cu(II) MOF, altering the band gap and light harvesting behavior. Owing to the tunable photoabsorption property resulting from the coordinating guests, photoinduced Reversible-deactivation radical polymerization (PRDRP) can be achieved to further simplify and fasten the polymerization.
More than the adjustable photoabsorption ability, the synergistic strategy via a combination of controlled/living polymerization technique and crystalline MOFs can be again evidenced as demonstrated in the MOF-based heterogeneous catalysts with enhanced dispersibility in solution. Through introducing hollow pollen pivots with surface immobilized environment-responsive polymer, PDMAEMA, highly dispersed MOF nanocrystals can be prepared after associating on polymer brushes via the intrinsic amine functionality in each DMAEMA monomer. Intriguingly, the pollen-PDMAEMA composite can serve as a “smart” anchor to trap nanoMOF particles with improved dispersibility, and thus to significantly enhance liquid-phase photocatalytic performance. Furthermore, the catalytic activity can be switched on and off via stimulable coil-to-globule transition of the PDMAEMA chains exposing or burying MOF catalytic sites, respectively.
Due to a challenging population growth and environmental changes, a need for new routes to provide required chemicals for human necessities arises. An effective solution discussed in this thesis is industrial heterogeneous catalysis. The development of an advanced industrial heterogeneous catalyst is investigated herein by considering porous carbon nano-material as supports and modifying their surface chemistry structure with heteroatoms. Such modifications showed a significant influence on the performance of the catalyst and provided a deeper insight regarding the interaction between the surface structure of the catalyst and the surrounding phase. This thesis contributes to the few present studies about heteroatoms effect on the catalyst performance and emphasizes on the importance of understanding surface structure functionalization in a catalyst in different phases (liquid and gaseous) and for different reactions (hydrogenolysis, oxidation, and hydrogenation/ polymerization). Herein, the heteroatoms utilized for the modifications are hydrogen (H), oxygen (O), and nitrogen (N). The heteroatoms effect on the metal particle size, on the polarity of the support/ the catalyst, on the catalytic performance (activity, selectivity, and stability), and on the interaction with the surrounding phase has been explored. First hierarchical porous carbon nanomaterials functionalized with heteroatoms (N) is synthesized and applied as supports for nickel nanoparticles for hydrogenolysis process of kraft lignin in liquid phase. This reaction has been performed in batch and flow reactors for three different catalysts, two of comparable hierarchical porosity, yet one is modified with N and the other is not, and a third is a prepared catalyst from a commercial carbon support. The reaction production and analyses show that the catalysts with hierarchical porosity perform catalytically much better than in presence of a commercial carbon support with lower surface area. Moreover, the modification with N-heteroatoms enhanced the catalytic performance because the heteroatom modified porous carbon material with nickel nanoparticles catalyst (Ni-NDC) performed highest among the other catalysts. In the flow reactor, Ni-NDC selectively degraded the ether bonds (β-O-4) in kraft lignin with an activity of 2.2 x10^-4 mg lignin mg Ni-1 s-1 for 50 h at 350°C and 3.5 mL min-1 flow, providing ~99 % conversion to shorter chained chemicals (mainly guaiacol derivatives). Then, the functionalization of carbon surface was further studied in selective oxidation of glucose to gluconic acid using < 1 wt. % of gold (Au) deposited on the previously-mentioned synthesized carbon (C) supports with different functionalities (Au-CGlucose, Au-CGlucose-H, Au-CGlucose-O, Au-CGlucoseamine). Except for Au-CGlucose-O, the other catalysts achieved full glucose conversion within 40-120 min and 100% selectivity towards gluconic acid with a maximum activity of 1.5 molGlucose molAu-1 s-1 in an aqueous phase at 45 °C and pH 9. Each heteroatom influenced the polarity of the carbon differently, affecting by that the deposition of Au on the support and thus the activity of the catalyst and its selectivity. The heteroatom effect was further investigated in a gas phase. The Fischer-Tropsch reaction was applied to convert synthetic gas (CO and H2) to short olefins and paraffins using surface-functionalized carbon nanotubes (CNTs) with heteroatoms as supports for ion (Fe) deposition in presence and absence of promoters (Na and S). The results showed the promoted Fe-CNT doped with nitrogen catalyst to be stable up to 180 h and selective to the formation of olefins (~ 47 %) and paraffins (~6 %) with a conversion of CO ~ 92 % at a maximum activity of 94 *10^-5 mol CO g Fe-1 s-1. The more information given regarding this topic can open wide range of applications not only in catalysis, but in other approaches as well. In conclusion, incorporation of heteroatoms can be the next approach for an advanced industrial heterogeneous catalyst, but also for other applications (e.g. electrocatalysis, gas adsorption, or supercapacitors).
The utilization of lignin as renewable electrode material for electrochemical energy storage is a sustainable approach for future batteries and supercapacitors. The composite electrode was fabricated from Kraft lignin and conductive carbon and the charge storage contribution was determined in terms of electrical double layer (EDL) and redox reactions. The important factors at play for achieving high faradaic charge storage capacity contribute to high surface area, accessibility of redox sites in lignin and their interaction with conductive additives. A thinner layer of lignin covering the high surface area of carbon facilitates the electron transfer process with a shorter pathway from the active sites of nonconductive lignin to the current collector leading to the improvement of faradaic charge storage capacity.
Composite electrodes from lignin and carbon would be even more sustainable if the fluorinated binder can be omitted. A new route to fabricate a binder-free composite electrode from Kraft lignin and high surface area carbon has been proposed by crosslinking lignin with glyoxal. A high molecular weight of lignin is obtained to enhance both electroactivity and binder capability in composite electrodes. The order of the processing step of crosslinking lignin on the composite electrode plays a crucial role in achieving a stable electrode and high charge storage capacity. The crosslinked lignin based electrodes are promising since they allow for more stable, sustainable, halogen-free and environmentally benign devices for energy storage applications. Furthermore, improvement of the amount of redox active groups (quinone groups) in lignin is useful to enhance the capacity in lithium battery applications. Direct oxidative demethylation by cerium ammonium nitrate has been carried out under mild conditions. This proves that an increase of quinone groups is able to enhance the performance of lithium battery. Thus, lignin is a promising material and could be a good candidate for application in sustainable energy storage devices.
Photocatalysis is considered significant in this new energy era, because the inexhaustibly abundant, clean, and safe energy of the sun can be harnessed for sustainable, nonhazardous, and economically development of our society. In the research of photocatalysis, the current focus was held by the design and modification of photocatalyst.
As one of the most promising photocatalysts, g-C3N4 has gained considerable attention for its eye-catching properties. It has been extensively explored in photocatalysis applications, such as water splitting, organic pollutant degradation, and CO2 reduction. Even so, it also has its own drawbacks which inhibit its further application. Inspired by that, this thesis will mainly present and discuss the process and achievement on the preparation of some novel photocatalysts and their photocatalysis performance. These materials were all synthesized via the alteration of classic g-C3N4 preparation method, like using different pre-compositions for initial supramolecular complex and functional group post-modification. By taking place of cyanuric acid, 2,5-Dihydroxy-1,4-benzoquinone and chloranilic acid can form completely new supramolecular complex with melamine. After heating, the resulting products of the two complex shown 2D sheet-like and 1D fiber-like morphologies, respectively, which maintain at even up to high temperature of 800 °C. These materials cover crystals, polymers and N-doped carbons with the increase of synthesis temperature. Based on their different pre-compositions, they show different dye degradation performances. For CLA-M-250, it shows the highest photocatalytic activity and strong oxidation capacity. It shows not only great photo-performance in RhB degradation, but also oxygen production in water splitting. In the post-modification method, a novel photocatalysis solution was proposed to modify carbon nitride scaffold with cyano group, whose content can be well controlled by the input of sodium thiocyanate. The cyanation modification leads to narrowed band gap as well as improved photo-induced charges separation. Cyano group grafted carbon nitride thus shows dramatically enhanced performance in the photocatalytic coupling reaction between styrene and sodium benzenesulfinate under green light irradiation, which is in stark contrast with the inactivity of pristine g-C3N4.
Vom Neandertal nach Afrika
(2018)
Spektakuläre Debatten um bedeutende Fossilienfunde begleiteten die Suche nach unseren Ursprüngen.
Wer waren die ersten Menschen? Nachdem die Antwort darauf lange mit der Schöpfungsgeschichte verbunden war, entflammten ab Mitte des 19. Jahrhunderts neuartige Debatten. Funde menschlicher Fossilien führten zu Auseinandersetzungen über den Ursprung der Menschheit. Umkämpft war nicht nur die Frage, ob die ersten Menschen Deutsche, Engländer, Europäer oder Asiaten waren, ob schwarz oder weiß. Es ging um das Wesen des Menschen. Knochen aus dem Neandertal, von Java oder Südafrika bilden bis heute eine Projektionsfläche für das Verständnis des menschlichen Selbst. Entsprechend intensiv waren die internationalen wissenschaftlichen und öffentlichen Debatten, bis sich in den 1950er Jahren die Idee eines gemeinsamen afrikanischen Ursprungs durchsetzte.
Ellinor Schweighöfer geht am Beispiel spektakulärer Funde der Suche nach dem Ursprung nach. Sie untersucht, welche Zuschreibungen die Funde auslösten und mit welchen Techniken sich wissenschaftliche Fakten etablierten. Es ist eine Wissensgeschichte, bei der viele Stimmen einbezogen werden - Wissenschaftler ebenso wie Massenmedien. So macht die Autorin auch die Wechselwirkungen zwischen Weltanschauung, Politik und Wissenschaft deutlich.
Funde und Fiktionen
(2018)
Urgeschichte im Fernsehen als Spiegel gesellschaftlicher Themen der Gegenwart. Unser gesichertes Wissen über die Urgeschichte der Menschheit ist angesichts der dünnen Quellenlage sehr begrenzt. Dennoch werden seit längerer Zeit sehr erfolgreiche Fernsehdokumentationen ausgestrahlt, die minutiös den Alltag in der fernsten menschlichen Vergangenheit präsentieren. Georg Koch untersucht, wie diese Darstellungen aus dem Zusammenspiel von Filmemachern und Wissenschaftlern entstanden und welchen Wandel sie seit den 1950er Jahren in der Bundesrepublik und in Großbritannien durchliefen. Er zeigt, wie Archäologen zu Medienstars des frühen britischen Fernsehens wurden, wie Hightech, Exotik und Abenteuer Einzug in die Darstellung der Archäologie hielten und wie inszenierte Erzählungen ein Millionenpublikum erreichten. Dabei wird deutlich, dass sich in den Betrachtungen der Urgeschichte stets Projektionen der Gegenwart finden, die zeitgemäße Antworten auf gesellschaftliche Fragen bieten.
Welle der Konsumgesellschaft
(2018)
Wie beeinflussten sich Massenmedien und Massenkonsum im Frankreich der Nachkriegszeit gegenseitig?
Radio Luxembourg war in der europäischen Rundfunklandschaft der Nachkriegszeit eine Ausnahme: Die privatkommerzielle Radiostation sendete werbefinanzierte Unterhaltungsprogramme in die benachbarten Staaten und erreichte damit ein Millionenpublikum. Die Autorin Anna Jehle zeigt anhand verschiedener Untersuchungsfelder - der Unternehmens- und Programmgeschichte, der Zielgruppen, der Marketingaktivitäten und des Werbezeitenverkaufs -, wie eng die Entwicklung der Konsumgesellschaft im Frankreich der sogenannten trente glorieuses mit der Verbreitung und Nutzung des Radios verbunden war. Mit seinem ganz auf Massenkonsum ausgerichteten Rundfunkkonzept war Radio Luxembourg nicht nur integraler Bestandteil, sondern auch Katalysator und Agent der Konsummoderne. Dies hatte weitreichende Auswirkungen für das französische Rundfunksystem, das sich unter dem Einfluss Radio Luxembourgs kommerzialisierte, und zwar bereits lange vor der Deregulierung des Rundfunks in den 1980er Jahren.
Geben oder Nehmen
(2018)
Geben oder nehmen? Diese Frage war nach der Wiedervereinigung nicht einfach zu beantworten. Die Euphorie über das Ende der deutschen Teilung 1989/90 wurde besonders frühzeitig und lang anhaltend von Konflikten überschattet, die sich an ungeklärten Eigentumsfragen an Grundstücken in Ostdeutschland entzündeten. Wohl kaum ein anderes Thema hat das Zusammenwachsen zwischen Ost und West so belastet wie die Kontroversen um die Rückübertragung von Eigentum.
Der Band bietet eine – bislang fehlende – ausgewogene Gesamtdarstellung der Eigentumsfragen im Kontext der Wiedervereinigung. Dazu gehört die Darstellungen der Vorbedingung der Eigentumsproblematik vor 1990, die Betrachtung der Entscheidungsfindung, die zum umstrittenen Grundsatz geführt hat, eine intensive Auseinandersetzung mit den Umsetzungsproblemen der gesetzlichen Regelungen in der Praxis sowie der Versuch, die Auswirkungen für die Region Berlin/Brandenburg zu bilanzieren.
Scalable data profiling
(2018)
Data profiling is the act of extracting structural metadata from datasets. Structural metadata, such as data dependencies and statistics, can support data management operations, such as data integration and data cleaning. Data management often is the most time-consuming activity in any data-related project. Its support is extremely valuable in our data-driven world, so that more time can be spent on the actual utilization of the data, e. g., building analytical models. In most scenarios, however, structural metadata is not given and must be extracted first. Therefore, efficient data profiling methods are highly desirable.
Data profiling is a computationally expensive problem; in fact, most dependency discovery problems entail search spaces that grow exponentially in the number of attributes. To this end, this thesis introduces novel discovery algorithms for various types of data dependencies – namely inclusion dependencies, conditional inclusion dependencies, partial functional dependencies, and partial unique column combinations – that considerably improve over state-of-the-art algorithms in terms of efficiency and that scale to datasets that cannot be processed by existing algorithms. The key to those improvements are not only algorithmic innovations, such as novel pruning rules or traversal strategies, but also algorithm designs tailored for distributed execution. While distributed data profiling has been mostly neglected by previous works, it is a logical consequence on the face of recent hardware trends and the computational hardness of dependency discovery.
To demonstrate the utility of data profiling for data management, this thesis furthermore presents Metacrate, a database for structural metadata. Its salient features are its flexible data model, the capability to integrate various kinds of structural metadata, and its rich metadata analytics library. We show how to perform a data anamnesis of unknown, complex datasets based on this technology. In particular, we describe in detail how to reconstruct the schemata and assess their quality as part of the data anamnesis.
The data profiling algorithms and Metacrate have been carefully implemented, integrated with the Metanome data profiling tool, and are available as free software. In that way, we intend to allow for easy repeatability of our research results and also provide them for actual usage in real-world data-related projects.
Die Folgen einer lebensmittelbedingten Erkrankung sind zum Teil gravierend, insbesondere für Kinder und immunsupprimierte Menschen. Hierbei gehören Salmonella und Campylobacter zu den häufigsten Erregern, die verantwortlich für gastrointestinale Erkrankungen in Deutschland sind. Trotz umfassender Maßnahmen der EU zur Prävention und Bekämpfung von Salmonellen in Geflügelbeständen und der Lebensmittel-Industrie, wird von einem stagnierenden Trend von Infektionszahlen berichtet. Zoonose-Erreger wie Salmonellen können über Nutztiere in die Nahrungskette des Menschen gelangen, wodurch sich Infektionsherde schnell ausbreiten können. Dabei sind bestehende Präventionsstrategien für Geflügel vorhanden, die aber nicht auf den Menschen übertragbar sind. Folglich sind Diagnostik und Prävention in der Lebensmittelindustrie essentiell. Deshalb besteht ein hoher Bedarf für spezifische, sensitive und zuverlässige Nachweismethoden, die eine Point-of-care Diagnostik gewährleisten. Durch ein wachsendes Verständnis der wirtsspezifischen Faktoren von S. enterica Serovaren kann die Entwicklung sowohl neuartiger diagnostischer Methoden, als auch neuartiger Therapien und Impfstoffe maßgeblich vorangetrieben werden.
Infolgedessen wurde in dieser Arbeit ein infektionsähnliches in vitro Modell für S. Enteritidis etabliert und darauf basierend eine umfassende Untersuchung zur Identifizierung neuer Zielstrukturen für den Erreger durchgeführt. Während einer Salmonellen-Infektion ist die erste zelluläre Barriere im Wirt die Epithelschicht. Dementsprechend wurde eine humane Zelllinie (CaCo 2, Darmepithel) für die Pathogen-Wirt-Studie ausgewählt. Das Salmonellen-Transkriptom und morphologische Eigenschaften der Epithelzellen wurden in verschiedenen Phasen der Salmonellen-Infektion untersucht und mit bereits gut beschriebenen Virulenzfaktoren und Beobachtungen in Bezug gesetzt. Durch dieses Infektionsmodell konnte ein spezifischer Phänotyp für die intrazellulären Salmonellen in den Epithelzellen nachgewiesen werden. Zudem wurde aufgezeigt, dass bereits die Kultivierung in Flüssigmedium einen invasionsaktiven Zustand der Salmonellen erzeugt. Allerdings wurde durch die Kokultivierung mit Epithelzellen eine zusätzliche Expression relevanter Gene induziert, um eine effiziente Adhäsion und Transmembran-Transport zu gewährleisten. Letzterer ist charakteristisch für die intrazelluläre Limitierung von Nährstoffen und prägt den infektionsrelevanten Status. Unter Berücksichtigung dieser Faktoren ergab sich ein Phänotyp, der eindeutig Mechanismen zur Wirtsadaptation und möglicherweise auch Pathogenese aufzeigt. Die intrazellulären Bakterien müssen vom Wirt separiert werden, was ein wesentlicher Schritt für Pathogen-bestimmende Analysen ist. Hierbei wurde mithilfe einer Detergenz-basierten Lyse der eukaryotischen Zellmembran und differentieller Zentrifugation, der eukaryotische Eintrag minimal gehalten. Unter Verwendung der Virulenz-adaptierten Salmonellen wurden Untersuchungen in Hinblick auf die Identifizierung neuer Zielstrukturen für S. Enteritidis durchgeführt. Mithilfe eines immunologischen Screenings wurden neue potentielle Antigene entdeckt. Zu diesem Zweck wurden bakterielle cDNA-basierte Expressionsbibliotheken hergestellt, die durch eine vereinfachte Microarray-Anwendung ein Hochdurchsatzscreening von Proteinen als potentielle Binder ermöglichen. Folglich konnten neue unbeschriebene Proteine identifiziert werden, die sich durch eine Salmonella-Spezifität oder Membranständigkeit auszeichnen. Ebenso wurde ein Vergleich der im Screening identifizierten Proteine mit der Regulation der kodierenden Gene im infektionsähnlichen Modell durchgeführt. Dabei wurde deutlich, dass die Häufigkeit von Transkripten einen Einfluss auf die Verfügbarkeit in der cDNA-Bibliothek und folglich auch auf die Expressionsbibliothek nimmt. Angesichts eines Ungleichgewichts zwischen der Gesamtzahl protein-kodierender Gene in S. Enteritidis zu möglichen Klonen, die während des Microarray-Screenings untersucht werden können, besteht der Bedarf einer Anreicherung von Proteinen in der Expressionsbibliothek. Das infektionsähnliche Modell zeigte, dass nicht nur Virulenz-assoziierte, sondern auch Stress- und Metabolismus-relevante Gene hochreguliert werden. Durch die Konstruktion dieser spezifischen cDNA-Bibliotheken ist die Erkennung von charakteristischen molekularen Markern gegeben.
Weiterhin wurden anhand der Transkriptomanalyse spezifisch hochregulierte Gene identifiziert, die relevant für das intrazelluläre Überleben von S. Enteritidis in humanen Epithelzellen sind. Hiervon wurden drei Gene näher untersucht, indem ihr Einfluss im infektionsähnlichen Modell mittels entsprechender Gen-Knockout-Stämme analysiert wurde. Dabei wurde für eine dieser Mutanten ein reduziertes Wachstum in der späten intrazellulären Phase nachgewiesen. Weiterführende in vitro Analysen sind für die Charakterisierung des Knockout-Stamms notwendig, um den Einsatz als potenzielles Therapeutikum zu verifizieren.
Zusammenfassend wurde ein in vitro Infektionsmodell für S. Enteritidis etabliert, wodurch neue Zielstrukturen des Erregers identifiziert wurden. Diese sind für diagnostische oder therapeutische Anwendungen interessant. Das Modell lässt sich ebenso für andere intrazelluläre Pathogene übertragen und gewährleistet eine zuverlässige Identifizierung von potentiellen Antigenen.
Nanophotonics is the field of science and engineering aimed at studying the light-matter interactions on the nanoscale. One of the key aspects in studying such optics at the nanoscale is the ability to assemble the material components in a spatially controlled manner. In this work, DNA origami nanostructures were used to self-assemble dye molecules and DNA coated plasmonic nanoparticles. Optical properties of dye nanoarrays, where the dyes were arranged at distances where they can interact by Förster resonance energy transfer (FRET), were systematically studied according to the size and arrangement of the dyes using fluorescein (FAM) as the donor and cyanine 3 (Cy 3) as the acceptor. The optimized design, based on steady-state and time-resolved fluorometry, was utilized in developing a ratiometric pH sensor with pH-inert coumarin 343 (C343) as the donor and pH-sensitive FAM as the acceptor. This design was further applied in developing a ratiometric toxin sensor, where the donor C343 is unresponsive and FAM is responsive to thioacetamide (TAA) which is a well-known hepatotoxin. The results indicate that the sensitivity of the ratiometric sensor can be improved by simply arranging the dyes into a well-defined array. The ability to assemble multiple fluorophores without dye-dye aggregation also provides a strategy to amplify the signal measured from a fluorescent reporter, and was utilized here to develop a reporter for sensing oligonucleotides. By incorporating target capturing sequences and multiple fluorophores (ATTO 647N dye molecules), a reporter for microbead-based assay for non-amplified target oligonucleotide sensing was developed. Analysis of the assay using VideoScan, a fluorescence microscope-based technology capable of conducting multiplex analysis, showed the DNA origami nanostructure based reporter to have a lower limit of detection than a single stranded DNA reporter. Lastly, plasmonic nanostructures were assembled on DNA origami nanostructures as substrates to study interesting optical behaviors of molecules in the near-field. Specifically, DNA coated gold nanoparticles, silver nanoparticles, and gold nanorods, were placed on the DNA origami nanostructure aiming to study surface-enhanced fluorescence (SEF) and surface-enhanced Raman scattering (SERS) of molecules placed in the hotspot of coupled plasmonic structures.
Deoxyribonucleic acid (DNA) is the carrier of human genetic information and is exposed to environmental influences such as the ultraviolet (UV) fraction of sunlight every day. The photostability of the DNA against UV light is astonishing. Even if the DNA bases have a strong absorption maximum at around 260 nm/4.77 eV, their quantum yield of photoproducts remains very low 1. If the photon energies exceed the ionization energy (IE) of the nucleobases ( ̴ 8-9 eV) 2, the DNA can be severely damaged. Photoexcitation and -ionization reactions occur, which can induce strand breaks in the DNA. The efficiency of the excitation and ionization induced strand breaks in the target DNA sequences are represented by cross sections. If Si as a substrate material is used in the VUV irradiation experiments, secondary electrons with an energy below 3.6 eV are generated from the substrate. This low energy electrons (LEE) are known to induce dissociative electron attachment (DEA) in DNA and with it DNA strand breakage very efficiently. LEEs play an important role in cancer radiation therapy, since they are generated secondarily along the radiation track of ionizing radiation.
In the framework of this thesis, different single stranded DNA sequences were irradiated with 8.44 eV vacuum UV (VUV) light and cross sections for single strand breaks (SSB) were determined. Several sequences were also exposed to secondary LEEs, which additionally contributed to the SSBs. First, the cross sections for SSBs depending on the type of nucleobases were determined. Both types of DNA sequences, mono-nucleobase and mixed sequences showed very similar results upon VUV radiation. The additional influence of secondarily generated LEEs resulted in contrast in a clear trend for the SSB cross sections. In this, the polythymine sequence had the highest cross section for SSBs, which can be explained by strong anionic resonances in this energy range. Furthermore, SSB cross sections were determined as a function of sequence length. This resulted in an increase in the strand breaks to the same extent as the increase in the geometrical cross section. The longest DNA sequence (20 nucleotides) investigated in this series, however, showed smaller cross section values for SSBs, which can be explained by conformational changes in the DNA. Moreover, several DNA sequences that included the radiosensitizers 5-Bromouracil (5BrU) and 8-Bromoadenine (8BrA) were investigated and the corresponding SSB cross sections were determined. It was shown that 5BrU reacts very strongly to VUV radiation leading to high strand break yields, which showed in turn a strong sequence-dependency. 8BrA, on the other hand, showed no sensitization to the applied VUV radiation, since almost no increase in strand breakage yield was observed in comparison to non-modified DNA sequences.
In order to be able to identify the mechanisms of radiation damage by photons, the IEs of certain DNA sequences were further explored using photoionization tandem mass spectrometry. By varying the DNA sequence, both the IEs depending on the type of nucleobase as well as on the DNA strand length could be identified and correlated to the SSB cross sections. The influence of the IE on the photoinduced reaction in the brominated DNA sequences could be excluded.
New bio-based polymers
(2018)
Redox-responsive polymers, such as poly(disulfide)s, are a versatile class of polymers with potential applications including gene- and drug-carrier systems. Their degradability under reductive conditions allows for a controlled response to the different redox states that are present throughout the body. Poly(disulfide)s are typically synthesized by step growth polymerizations. Step growth polymerizations, however, may suffer from low conversions and therefore low molar masses, limiting potential applications. The purpose of this thesis was therefore to find and investigate new synthetic routes towards the synthesis of amino acid-based poly(disulfide)s.
The different routes in this thesis include entropy-driven ring opening polymerizations of novel macrocyclic monomers, derived from cystine derivatives. These monomers were obtained with overall yields of up to 77% and were analyzed by mass spectrometry as well as by 1D and 2D NMR spectroscopy. The kinetics of the entropy-driven ring-opening metathesis polymerization (ED-ROMP) were thoroughly investigated in dependence of temperature, monomer concentration, and catalyst concentration. The polymerization was optimized to yield poly(disulfide)s with weight average molar masses of up to 80 kDa and conversions of ~80%, at the thermodynamic equilibrium. Additionally, an alternative metal free polymerization, namely the entropy-driven ring-opening disulfide metathesis polymerization (ED-RODiMP) was established for the polymerization of the macrocyclic monomers. The effect of different solvents, concentrations and catalyst loadings on the polymerization process and its kinetics were studied. Polymers with very high weight average molar masses of up to 177 kDa were obtained. Moreover, various post-polymerization reactions were successfully performed.
This work provides the first example of the homopolymerization of endo-cyclic disulfides by ED-ROMP and the first substantial study into the kinetics of the ED-RODiMP process.
Utilization of sunlight for energy harvesting has been foreseen as sustainable replacement for fossil fuels, which would also eliminate side effects arising from fossil fuel consumption such as drastic increase of CO2 in Earth atmosphere. Semiconductor materials can be implemented for energy harvesting, and design of ideal energy harvesting devices relies on effective semiconductor with low recombination rate, ease of processing, stability over long period, non-toxicity and synthesis from abundant sources. Aforementioned criteria have attracted broad interest for graphitic carbon nitride (g-CN) materials, metal-free semiconductor which can be synthesized from low cost and abundant precursors. Furthermore, physical properties such as band gap, surface area and absorption can be tuned. g-CN was investigated as heterogeneous catalyst, with diversified applications from water splitting to CO2 reduction and organic coupling reactions. However, low dispersibility of g-CN in water and organic solvents was an obstacle for future improvements.
Tissue engineering aims to mimic natural tissues mechanically and biologically, so that synthetic materials can replace natural ones in future. Hydrogels are crosslinked networks with high water content, therefore are prime candidates for tissue engineering. However, the first requirement is synthesis of hydrogels with mechanical properties that are matching to natural tissues. Among different approaches for reinforcement, nanocomposite reinforcement is highly promising.
This thesis aims to investigate aqueous and organic dispersions of g-CN materials. Aqueous g-CN dispersions were utilized for visible light induced hydrogel synthesis, where g-CN acts as reinforcer and photoinitiator. Varieties of methodologies were presented for enhancing g-CN dispersibility, from co-solvent method to prepolymer formation, and it was shown that hydrogels with diversified mechanical properties (from skin-like to cartilage-like) are accessible via g-CN utilization. One pot photografting method was introduced for functionalization of g-CN surface which provides functional groups towards enhanced dispersibility in aqueous and organic media. Grafting vinyl thiazole groups yields stable additive-free organodispersions of g-CN which are electrostatically stabilized with increased photophysical properties. Colloidal stability of organic systems provides transparent g-CN coatings and printing g-CN from commercial inkjet printers.
Overall, application of g-CN in dispersed media is highly promising, and variety of materials can be accessible via utilization of g-CN and visible light with simple chemicals and synthetic conditions. g-CN in dispersed media will bridge emerging research areas from tissue engineering to energy harvesting in near future.
Understanding how humans move their eyes is an important part for understanding the functioning of the visual system. Analyzing eye movements from observations of natural scenes on a computer screen is a step to understand human visual behavior in the real world. When analyzing eye-movement data from scene-viewing experiments, the impor- tant questions are where (fixation locations), how long (fixation durations) and when (ordering of fixations) participants fixate on an image. By answering these questions, computational models can be developed which predict human scanpaths. Models serve as a tool to understand the underlying cognitive processes while observing an image, especially the allocation of visual attention.
The goal of this thesis is to provide new contributions to characterize and model human scanpaths on natural scenes. The results from this thesis will help to understand and describe certain systematic eye-movement tendencies, which are mostly independent of the image. One eye-movement tendency I focus on throughout this thesis is the tendency to fixate more in the center of an image than on the outer parts, called the central fixation bias. Another tendency, which I will investigate thoroughly, is the characteristic distribution of angles between successive eye movements.
The results serve to evaluate and improve a previously published model of scanpath generation from our laboratory, the SceneWalk model. Overall, six experiments were conducted for this thesis which led to the following five core results:
i) A spatial inhibition of return can be found in scene-viewing data. This means that locations which have already been fixated are afterwards avoided for a certain time interval (Chapter 2).
ii) The initial fixation position when observing an image has a long-lasting influence of up to five seconds on further scanpath progression (Chapter 2 & 3).
iii) The often described central fixation bias on images depends strongly on the duration of the initial fixation. Long-lasting initial fixations lead to a weaker central fixation bias than short fixations (Chapter 2 & 3).
iv) Human observers adjust their basic eye-movement parameters, like fixation dura- tions and saccade amplitudes, to the visual properties of a target they look for in visual search (Chapter 4).
v) The angle between two adjacent saccades is an indicator for the selectivity of the upcoming saccade target (Chapter 4).
All results emphasize the importance of systematic behavioral eye-movement tenden- cies and dynamic aspects of human scanpaths in scene viewing.
Arctic warming has implications for the functioning of terrestrial Arctic ecosystems, global climate and socioeconomic systems of northern communities. A research gap exists in high spatial resolution monitoring and understanding of the seasonality of permafrost degradation, spring snowmelt and vegetation phenology. This thesis explores the diversity and utility of dense TerraSAR-X (TSX) X-Band time series for monitoring ice-rich riverbank erosion, snowmelt, and phenology of Arctic vegetation at long-term study sites in the central Lena Delta, Russia and on Qikiqtaruk (Herschel Island), Canada. In the thesis the following three research questions are addressed:
• Is TSX time series capable of monitoring the dynamics of rapid permafrost degradation in ice-rich permafrost on an intra-seasonal scale and can these datasets in combination with climate data identify the climatic drivers of permafrost degradation?
• Can multi-pass and multi-polarized TSX time series adequately monitor seasonal snow cover and snowmelt in small Arctic catchments and how does it perform compared to optical satellite data and field-based measurements?
• Do TSX time series reflect the phenology of Arctic vegetation and how does the recorded signal compare to in-situ greenness data from RGB time-lapse camera data and vegetation height from field surveys?
To answer the research questions three years of TSX backscatter data from 2013 to 2015 for the Lena Delta study site and from 2015 to 2017 for the Qikiqtaruk study site were used in quantitative and qualitative analysis complimentary with optical satellite data and in-situ time-lapse imagery.
The dynamics of intra-seasonal ice-rich riverbank erosion in the central Lena Delta, Russia were quantified using TSX backscatter data at 2.4 m spatial resolution in HH polarization and validated with 0.5 m spatial resolution optical satellite data and field-based time-lapse camera data. Cliff top lines were automatically extracted from TSX intensity images using threshold-based segmentation and vectorization and combined in a geoinformation system with manually digitized cliff top lines from the optical satellite data and rates of erosion extracted from time-lapse cameras. The results suggest that the cliff top eroded at a constant rate throughout the entire erosional season. Linear mixed models confirmed that erosion was coupled with air temperature and precipitation at an annual scale, seasonal fluctuations did not influence 22-day erosion rates. The results highlight the potential of HH polarized X-Band backscatter data for high temporal resolution monitoring of rapid permafrost degradation.
The distinct signature of wet snow in backscatter intensity images of TSX data was exploited to generate wet snow cover extent (SCE) maps on Qikiqtaruk at high temporal resolution. TSX SCE showed high similarity to Landsat 8-derived SCE when using cross-polarized VH data. Fractional snow cover (FSC) time series were extracted from TSX and optical SCE and compared to FSC estimations from in-situ time-lapse imagery. The TSX products showed strong agreement with the in-situ data and significantly improved the temporal resolution compared to the Landsat 8 time series. The final combined FSC time series revealed two topography-dependent snowmelt patterns that corresponded to in-situ measurements. Additionally TSX was able to detect snow patches longer in the season than Landsat 8, underlining the advantage of TSX for detection of old snow. The TSX-derived snow information provided valuable insights into snowmelt dynamics on Qikiqtaruk previously not available.
The sensitivity of TSX to vegetation structure associated with phenological changes was explored on Qikiqtaruk. Backscatter and coherence time series were compared to greenness data extracted from in-situ digital time-lapse cameras and detailed vegetation parameters on 30 areas of interest. Supporting previous results, vegetation height corresponded to backscatter intensity in co-polarized HH/VV at an incidence angle of 31°. The dry, tall shrub dominated ecological class showed increasing backscatter with increasing greenness when using the cross polarized VH/HH channel at 32° incidence angle. This is likely driven by volume scattering of emerging and expanding leaves. Ecological classes with more prostrate vegetation and higher bare ground contributions showed decreasing backscatter trends over the growing season in the co-polarized VV/HH channels likely a result of surface drying instead of a vegetation structure signal. The results from shrub dominated areas are promising and provide a complementary data source for high temporal monitoring of vegetation phenology.
Overall this thesis demonstrates that dense time series of TSX with optical remote sensing and in-situ time-lapse data are complementary and can be used to monitor rapid and seasonal processes in Arctic landscapes at high spatial and temporal resolution.
Mitöffentlichkeit
(2018)
Im Mittelpunkt dieser beziehungsgeschichtlichen Darstellung steht die Geschichte der deutsch-deutschen Arbeit der Evangelischen Akademie Berlin-Brandenburg seit ihrer Gründung 1951 bis Ende der 1970er- bzw. Anfang der 1980er-Jahre. Nach einem Überblick zur Geschichte der Ev. Akademien und der Evangelischen Akademie Berlin-Brandenburg wird sie als ein exemplarischer deutsch-deutscher Ort literarischer Kommunikation, der „Vergangenheitsbewältigung“ und des christlich-jüdischen Dialogs als Teil der NS-Auseinandersetzung beschrieben. Im Rahmen der literarischen Arbeit wurden häufig in der DDR – noch – nicht veröffentlichte westdeutsche und westeuropäische Texte in den literarischen Kreislauf eingespeist; hiermit konstitutiv verbunden ist das ebenfalls hochpolitische und gesamtdeutsch dimensionierte Thema der Vergangenheitsbewältigung. Über den Kontext der Akademie hinaus versteht sich die Arbeit auch als ein Beitrag zur deutsch-deutschen Geschichte der Vergangenheitsbewältigung. Mit den seit 1961 durchgeführten Israel-Tagungen institutionalisierte sich der christlich-jüdische Dialog etwa 15 Jahre früher als in der evangelischen Kirche in der DDR. Damit bietet diese Arbeit auch neue Aspekte der Geschichte des Protestantismus in Ostdeutschland und der christlich-jüdischen Beziehungen in der DDR. Hinsichtlich der kirchlichen Vergangenheitsbewältigung leistete die Akademie Pionierarbeit. Im Horizont deutschland-, kultur- und kirchenpolitischer Entwicklungen schwächte sich ab Ende der 1960er-Jahre der gesamtdeutsche Bezug ab. Die Akademie war durch Nähe und Distanz zu staatlichen und kirchlichen Kontexten geprägt. Massive Überwachungen durch die Staatssicherheit und Konflikte mit staatlichen Organen sind Ausdruck dieses „Eigen-Sinns“. Als christlicher Akteur beharrte die Akademie auf Mitgestaltung und Mitwirkung und erzeugte durch ihre Arbeit Mitöffentlichkeit. Dieser neu eingeführte Begriff entzieht sich dem Dualismus von offizieller Öffentlichkeit und Gegenöffentlichkeit und leistet eine wesentliche Differenzierung des Formenkreises von Öffentlichkeit in der DDR.