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    <title>OPUS 4 Latest Documents RSS Feed</title>
    <description>Latest documents</description>
    <link>http://opus4.kobv.de/opus4-ubbayreuth/index/index/</link>
    <pubDate>Wed, 15 May 2013 10:21:39 +0200</pubDate>
    <lastBuildDate>Wed, 15 May 2013 10:21:39 +0200</lastBuildDate>
    <item>
      <title>Interactions between hydrology and biogeochemistry within riparian wetlands</title>
      <link>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1189</link>
      <description>Interactions between hydrology and biogeochemistry at various spatio-temporal scales are important control mechanisms within terrestrial and aquatic ecosystems and exist among different compartments and transition interfaces. Understanding the fundamental mechanistic couplings between hydrological and biogeochemical processes and how these couplings feed back into ecosystem services and functions is an interdisciplinary challenge that must be addressed especially in the context of humanly mediated climate change. Riparian wetlands, as a transition zone between terrestrial and aquatic ecosystems, occupy large fractions of terrestrial ecosystems and provide important ecohydrological services. Due to their anoxic environments, riparian wetlands are able to store significant amounts of carbon as peat and act as an effective nutrient sink e.g. for sulfur, phosphorous and nitrogen. Riparian wetlands are characterized by highly dynamical interactions between hydrologically controlled transport mechanisms and biogeochemically controlled substrate availability, which governs nutrient cycling as well as the sink and source functions of wetlands. Generally, these interactions and their potential implications on ecosystem functions are only poorly understood. The representation of the tight couplings between hydrology and biogeochemistry in mechanistic models is a very challenging task because they have revealed a complexity which is often beyond the capabilities of current models. The objective of this thesis is to investigate interactions between hydrology and biogeochemistry in riparian wetlands and to understand their potential implications for internal biogeochemical process distributions and solute mobilization. Additionally, one major focus of the thesis is the attempt to represent such fundamental couplings in a process-based, hydrological/biogeochemical modeling approach. To this end, this thesis uses a combination of field and virtual experiments, as well as catchment-scale numerical modeling, performed for the Lehstenbach catchment, which was exemplarily chosen as main study site. &#13;
Results from the virtual experiments show very complex small-scale hydrological dynamics within the riparian areas. Here, runoff generation processes are strongly influenced by the spatial structure of the wetland-typical micro-topography (hummocks and hollows). Surface flow is episodically generated by a highly dynamical, threshold-controlled process where extended surface flow networks drain large fractions of the wetland's area. During intensive rainstorm events these surface flow networks, which contribute to stream discharge due to a fill and spill mechanism, dominate runoff generation. These fast flow components are characterized by very low residence times (minutes to hours) and once they are activated, the surface flow networks are able to rapidly mobilize large amounts of solutes, like nitrate or dissolved organic carbon (DOC), out of the wetlands by bypassing deeper anoxic layers. The importance of fast flow components for the catchment-scale mobilization of DOC was further confirmed by field investigations and catchment-scale numerical modeling. High frequency measurements of DOC in runoff of the Lehstenbach catchment revealed that DOC export is subject to substantial short term variations at an hourly to daily timescale. During intense rainstorms, DOC concentrations are up to ten times higher (up to 40 mg/L) compared to low flow conditions (~3-5 mg/L). Short term variations together with the dramatic rise of DOC concentrations in runoff during rainstorms can be explained by the episodically activation of fast flow components in the wetland areas. At the catchment-scale, application of a hydraulic mixing-cell (HMC) methodology in combination with numerical modeling has revealed that fast flow components like saturated overland flow are exclusively generated in the wetland areas during intensive rainstorm events. On an annual basis, exemplarily for the hydrological year 2001, the HMC analysis quantified the relative contribution of saturated overland flow related to the total discharge with 19.5%, which highlights the importance of riparian wetlands for catchment-scale runoff generation. &#13;
Virtual experiments, additionally show that distinct shifts between surface and subsurface flow dominance, as a result of small-scale micro-topographic driven runoff generation in the wetlands, are responsible for very complex three-dimensional subsurface flow patterns showing a wide range of subsurface residence times. To investigate how these micro-topography induced subsurface flow patterns, together with the non-uniform hydrological and biogeogeochemical boundary conditions, affect the internal re-distribution and transformation of redox-sensitive species (like nitrate, sulfate or iron) a coupled hydrological/biogeogeochemical model was developed. In the model, wetland-typical biogeochemical processes are represented in a sequential stream tube approach where redox-sensitive processes are implemented as kinetic reactions. Simulations show the formation of local hot spots for redox-sensitive processes within the subsurface as a result of the complex subsurface flow paths and the transport-limited availability of electron acceptors and donors. Formation of hot spots was simulated for all key reduction processes including iron(III)-/sulfate reduction and denitrification as well as for the corresponding re-oxidation processes. These results offer a new perspective on hydrologically controlled biogeochemical transformation processes in riparian wetlands, which provides a dynamic framework to explain process heterogeneity in wetland soils and variability in process rates over space and time. &#13;
Findings from this thesis clearly prove how useful interdisciplinary approaches are in understanding processes and mechanisms in ecosystems and how important functions of ecosystems are affected by couplings among those. However, a lot of knowledge gaps still exist in understanding the nature of dependency between water and nutrient cycles across scales and how these interacting cycles feed back into humanly-mediated climate change in ecosystems. Development of new interdisciplinary methodologies and frameworks as well as an integrated way of thinking across the boundaries of the different environmental disciplines is necessary to address the grand challenges associated with climate change.&#13;
</description>
      <author>Sven Frei</author>
      <category>doctoralthesis</category>
      <guid>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1189</guid>
      <pubDate>Wed, 15 May 2013 10:21:39 +0200</pubDate>
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      <title>Über lasergeheizte kolloidale Goldnanopartikel in Polymerlösungen</title>
      <link>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1186</link>
      <description>Im Rahmen dieser Arbeit wurden verschiedene Aspekte untersucht, die im Zusammenhang mit photothermischen Effekten durch absorbierende Goldkollide in binären Polymerlösungen stehen. Dabei kamen neben den experimentellen Untersuchungen durch Hellfeld- und Phasenkontrastmikroskopie in Verbindung mit lokalen Laserheizungen und Methoden der CCD-Einzelteilchenverfolgung auch numerische Verfahren zur Lösung von Differentialgleichungen zum Einsatz.&#13;
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Das durch Absorption von Laserlicht erzeugte Temperaturfeld isolierter Goldnanopartikel wurde analytisch und die Abweichungen vom Idealfall eines unendlich ausgedehnten Mediums homogener Wärmeleitung mit Comsol für spezielle Geometrien und Grenzfälle berechnet.&#13;
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Nach diesen Untersuchungen in isothermen Systemen wurde dann die Käfigbildung um geheizte Goldkolloide in Polymerlösungen untersucht. Zur theoretischen Beschreibung des System Polystyrol/Toluol wurde der Soret-Koeffizient als Funktion der Konzentration, Molmasse und Temperatur parametrisiert. Dabei wurden neben Literaturwerten für die Molmassenabhängigkeit auch eigene Messungen der Transportkoeffizienten für die Temperatur- und Konzentrationsabhängigkeit verwendet. Die Parametrisierung des Soret-Koeffizienten reproduziert in den essentiellen Grenzfällen großer und kleiner Konzentrationen die erwarteten Skalengesetze und das Verschwinden der Molmassenabhängigkeit. Das durch den Soret-Effekt hervorgerufene Konzentrationsfeld konnte dann durch die numerische Integration der erweiterten Diffusionsgleichung berechnet werden. Aufgrund der komplexen Temperatur-, Konzentrations- und Molmassenabhängigkeit dieses Prozesses stehen die Selbstverstärkung und Schwächung der Konzentrationsabreicherung im Wettbewerb. Die Konzentration in der nahen Umgebung der Heizquelle kann, in Abhängigkeit von der Gleichgewichtskonzentration und der Molmasse, stark reduziert oder sogar auf praktisch Null reduziert werden. Die Konzentration für verschiedene Parameter wie Abstand, Molmasse und Oberflächentemperatur wurden berechnet und visualisiert.&#13;
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Der Soret-Koeffizient des Systems Pullulan/Wasser weist temperaturabhängig einen Nulldurchgang auf. Dadurch entstehen komplizierte Szenarien zur Strukturbildung. Das Konzentrationsfeld wurde numerisch berechnet und diskutiert. Im Gegensatz zum Konzentrationsfeld von PS/Toluol ist es für Pullulan/Wasser nicht mehr monoton, sondern zeigt neben eines starken Ausbleichens in der unmittelbaren Umgebung des Kolloids ein Konzentrationsmaximum oberhalb der Gleichgewichtskonzentration auf. &#13;
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Da die Dynamik eingebetteter Goldkolloide von der lokalen Viskosität abhängt, wurden zwei Szenarien im System PS/Toluol diskutiert: bei hohen Polymerkonzentrationen, wo die Lösung in die Nähe des Glasübergangs kommt, sorgen sowohl die Abreicherung des Polymers als auch die dadurch bedingte Vergrößerung des Abstandes zur Glastemperatur für eine Abnahme der Viskosität. Dieser Effekt ist mit einer abschwächenden Rückkopplung verbunden und die Polymerkonzentration auf der Teilchenoberfläche bleibt endlich, unabhängig von der Molmasse im Hochpolymer-Regime. Das zweite Szenario beschreibt die Viskosität von Lösungen mit langen Ketten im halb-verdünnten Bereich. Dort findet man Selbstverstärkung aufgrund des zunehmenden Soret-Koeffizienten und das Polymer kann auch schon für moderate Temperaturerhöhungen vollständig von der Oberfläche verdrängt werden.&#13;
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Es konnte weiterhin gezeigt werden, dass sich Goldnanopartikel als Markierungen eignen, um über ein einzelnes, geheiztes Kolloid thermooptisch induzierte Netzwerkdeformationen mittels Lichtmikroskopie sichtbar zu machen. Auf Zeitskalen des Experiments, in denen das verschlaufte, transiente Polymernetzwerk bestehen bleibt und die Kolloide daher in den Netzwerkmaschen praktisch immobil sind, kann durch Einzelteilchenverfolgung die Verschiebung der Kolloide mit dem Deformationsfeld des Netzwerkes korreliert werden. In realistischen Geometrien nimmt die Verschiebung aufgrund der Randbedingungen mit steigendem Abstand zwar (in erster Näherung linear) ab, bleibt aber langreichweitig. Die Modellierung dieser Geometrie erfolgte über die Vorstellung zweier impermeabler konzentrischer Kugeln. Trotz dieses recht einfachen Modells konnte eine gute Übereinstimmung zwischen Messung und numerisch berechneten Verschiebungen gefunden werden.</description>
      <author>Florian Schwaiger</author>
      <category>doctoralthesis</category>
      <guid>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1186</guid>
      <pubDate>Fri, 03 May 2013 10:12:24 +0200</pubDate>
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      <title>The Re-implementation of Sharia in Northern Nigeria and the Education of Muslim Women 1999-2007</title>
      <link>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1134</link>
      <description>This study investigates the impact of the re-implementation of Sharia on the education of Muslim women between 1999 and 2007, in four states in northern Nigeria namely, Zamfara, Kano, Bauchi and Kaduna. The study fills the research gap in the description of the status of women with respect to education under the Sharia dispensation re-introduced in 1999. Before this era, scholarly works have documented the state of female education in northern Nigeria; however, none deals directly with post re-implementation and its impact on Muslim women’s education. This period is particularly interesting because it coincides with the return of the country to democratic rule after a string of military rules. Using interviews with Sharia proponents, school administrators, women and reports from Sharia Commissions in these states, the work establishes that while Zamfara and Kano States underwent transformations in the educational sector as a result of the programs introduced by the Sharia governments, the changes in the educational domain in Bauchi and Kaduna were exceedingly triggered by the return of democracy in Nigeria after decades of military rule. The results arrived at in this study reveal interesting facets of the relationship between Sharia and the education of Muslim women. The research shows that proponents of Sharia used the premise (also supported by verses from the Qur’an and Prophet Mohammed’s teachings) that education is an important part of Islam to which both males and females have equal rights, to sell the Islamic-based educational programs introduced by the Sharia regime. Using religion to promote these programs, the predominantly male Sharia bodies, mitigate the often tough cultural practices and religious dogmas that have prevented women from having full access to formal, western education. However, the type of education offered to women under these Sharia programs is a hybrid of formal education and Islamic education which pays strict attention to such cultural and religious practices like the wearing of the hijab, the separation of males and females in schools, the teaching of practical, home craft skills such as knitting and baking to the women. So, instead of the education taking women out of the home domain in which they have been restricted in the past, it rather further maintains them while providing them access to formal education which they will hardly use in any public career. &#13;
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</description>
      <author>Chikas Danfulani</author>
      <category>doctoralthesis</category>
      <guid>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1134</guid>
      <pubDate>Tue, 30 Apr 2013 10:38:02 +0200</pubDate>
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      <title>Crystalline-core micelles based on triblock terpolymers with polyethylene middle blocks</title>
      <link>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1157</link>
      <description>This thesis is focused on the crystallization-induced structure formation of polyethylene containing triblock terpolymers in organic solvents to surface-compartmentalized worm-like crystalline-core micelles (wCCMs). Obtaining profound knowledge of the parameters controlling the self-assembly process allowed the production of a variety of complex one-dimensional micellar architectures with many potential applications, such as adaptive surfactants.&#13;
At first, the basic parameters that control the crystallization-induced self-assembly were explored using symmetric polystyrene-block-polyethylene-block-poly(methyl methacrylate) (PS-b-PE-b-PMMA) triblock terpolymers and a PS-b-PE-b-PS triblock copolymer. In good solvents for the PE block, e.g. THF and toluene, the selective formation of wCCMs was observed over a wide range of concentration, applied crystallization temperature and polymer composition. Whereas wCCMs produced by PS-b-PE-b-PS showed a homogeneous PS corona, a patch-like compartmentalization of the corona was observed if the micelles were formed by PS-b-PE-b-PMMA. As THF shows equal solvent quality for both corona blocks, wCCMs with almost alternating PS and PMMA compartments of about 15 nm were observed in this solvent. However, if structure formation was conducted in bad solvents for PE, such as dioxane or dimethylacetamide, spherical micelles with amorphous PE cores were formed already before crystallization. Hence, the subsequent crystallization of PE resulted in spherical CCMs with a patchy or a homogeneous corona depending on the used triblock. These findings allow the highly selective production of stable spherical or worm-like CCMs from the same polymer.&#13;
As the corona structure of the patchy micelles self-assembled from triblock terpolymers was mainly deduced from transmission electron microscopy (TEM) performed on dried samples, a small-angle neutron scattering (SANS) study was performed in order to elucidate the morphology in solution. Therefore a partly deuterated triblock terpolymer was synthesized and measured at different contrasts to allow the selective detection of the different corona compartments. The resulting SANS curves could be interpreted using a form factor model for core-shell cylinders with alternating PS and PMMA hemishells including interparticle interactions, thus validating the TEM observations. Notably, Janus-type and patchy cylinders can be clearly distinguished using the applied form factor model.&#13;
Moreover, the controlled formation of wCCMs with tunable corona composition and structure was achieved using the cocrystallization of different triblock copolymers. Via random cocrystallization of PS-b-PE-b-PMMA and PS-b-PE-b-PS the corona morphology could be tuned continuously from a mixed corona at low PMMA content over spherical PMMA patches of increasing number and size to alternating PS and PMMA patches. This approach allows to manufacture wCCMs with predefined corona structure omitting the need to synthesize a new tailor-made triblock terpolymer for every desired morphology.&#13;
By establishing the controlled crystallization-driven self-assembly of triblock terpolymers with PE middle blocks, it was further possible to prepare wCCMs with predefined average lengths up to 500 nm and length polydispersities as low as Lw/Ln = 1.1. Here, self-assembled spherical CCMs of PS-b-PE-b-PS were used as seeds for the controlled growth of PS-b-PE-b-PS unimers. Upon further addition of PS-b-PE-b-PMMA unimers these grew epitaxially onto the preexisting wCCMs, resulting in triblock co-micelles that consisted of middle blocks with a homogeneous PS corona and outer blocks with alternating PS/PMMA compartments. These structures represent not only the first block co-micelles including blocks with a patchy corona, but also the first ones produced from purely organic block copolymers.&#13;
In view of application, the ability of patchy wCCMs formed by PS-b-PE-b-PMMA to stabilize interfaces was investigated using pendant-drop tensiometry. The observed reduction of the interfacial tension at the toluene/water interface was significantly higher than that of comparable triblock terpolymer single chains and that of wCCMs with a homogeneous PS corona. Interestingly, the obtained equilibrium interfacial tension equaled that of Janus cylinders with similar dimensions. To explain this unexpected finding the corona chains were proposed to adapt to the interface via selective collapse and shielding of the incompatible part of the corona chains. Studying wCCMs formed by several triblock terpolymers with different compositions, the interfacial activity was found to increase with increasing overall length of the corona chains, and to a certain extent with the molar fraction of PS units in the corona.</description>
      <author>Joachim Schmelz</author>
      <category>doctoralthesis</category>
      <guid>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1157</guid>
      <pubDate>Fri, 26 Apr 2013 10:49:07 +0200</pubDate>
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    <item>
      <title>Applicability of weight-shift microlight aircraft for measuring the turbulent exchange above complex terrain</title>
      <link>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1143</link>
      <description>The possibility to reliably observe the exchange of heat and moisture between the land surface and the atmosphere is vital to our understanding of the regional and global cycling of energy and water. While ground-based flux measurements can be made continuously for long periods, they only represent a small landscape unit. On the other hand, aircraft-based measurements have the ability to directly measure the exchange over large areas. Especially over heterogeneous landscapes the spatio-temporal characteristics of both approaches complement each other. However, complex terrestrial ecosystems are sparsely investigated to date, in particular over topographically structured terrain. This can be attributed to; (i) limitations in the description of boundary layer processes over non-homogenous terrain, and (ii) a lack of applicable measurement platforms and techniques to study these processes. In pursue of a resolution strategy, this dissertation investigates the applicability of weight-shift microlight aircraft (WSMA) to gain new insights in the spatial variability of heat and moisture exchange over complex terrain.&#13;
WSMA are comparatively cheap in procurement and maintenance, and their unique structure provides exceptional transportability and climb rate. These structural features qualify the WSMA for terrain-following flight over complex and inaccessible terrain, but potentially influence measurements aboard the aircraft. In this dissertation a WSMA with a scientific payload enabling fast measurements of the 3D wind, temperature, water vapor concentration, position, and the radiative flux is used to;&#13;
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(i) Quantify the WSMA wind measurement uncertainty. A novel time-domain procedure is developed, which improves the accuracy of the WSMA wind measurement by 63% for the horizontal- and 72% for the vertical wind components. The resulting precisions are ±0.09 m s−1 and ±0.04 m s−1, and the agreement with ground-based measurements is in the order of ±0.4 m s−1 and ±0.3 m s−1 (root mean square deviation), respectively.&#13;
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(ii) Quantify the WSMA eddy-covariance flux measurement uncertainty. From uncertainty propagation the smallest resolvable changes in friction velocity (0.02 m s−1), and sensible- (5 W m−2) and latent (3 W m−2) heat flux are estimated. In comparison to tower measurements, the WSMA observes higher fluxes (17–21%). The differences are not statistically significant, and can be explained by the tower setup and non-propagating eddies.&#13;
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(iii) Spatially resolve and regionalize the heat and moisture exchange above a complex landscape. Wavelet decomposition of the turbulence data is used to yield a flux observation each 90 m along the flight path. For each flux observation the biophysical surface properties in the flux footprint are determined. An environmental response function between the flux observations and biophysical and meteorological drivers is then inferred using a machine learning technique. This function is used to produce regional maps of the heat and moisture exchange to an accuracy of ≤18% and a precision of ≤5% for individual land covers.&#13;
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Hence this dissertation provides the necessary basis for using WSMA to investigate the mechanisms of turbulent exchange over heterogeneous and topographically structured terrain. Moreover, the developed algorithms are generally applicable to (i) partitioning flux uncertainty and environmental variability, (ii) extrapolating flux measurements, (iii) assessing the spatial representativeness of long-term tower flux measurements, and (iv) designing, constraining and evaluating flux algorithms for remote sensing and numerical modeling applications.</description>
      <author>Stefan Metzger</author>
      <category>doctoralthesis</category>
      <guid>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1143</guid>
      <pubDate>Thu, 18 Apr 2013 09:11:09 +0200</pubDate>
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      <title>Effects of copper on calcium metabolism and detoxification mechanisms in freshwater bivalve species of Anodonta</title>
      <link>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1138</link>
      <description>Copper (Cu) is one of the metals contaminating European fresh water ecosystems. Filter feeding bivalves have high bioaccumulation potential for transition metals as Cu. While copper is an essential micronutrient for living organisms, it causes serious metabolic and physiological impairments when in excess.&#13;
The objectives of this thesis are to get knowledge on toxic effects and detoxification mechanisms of copper in Anodonta cygnea and Anodonta anatina, two mussel species widely distributed in continental waters. Because Ca plays a fundamental role in shell formation and in numerous biological processes, Cu2+ effects on cellular plasma membrane calcium transport were studied first. In the second step, the investigations focused on Cu2+ detoxification mechanism involving cysteine (Cys) rich compounds known to play a major role in homeostasis of essential trace metals and in cellular metal detoxification.&#13;
Under our experimental conditions, copper inhibition of Ca2+-ATPase activity was observed in the gills and the kidneys, and inhibition of Na+/K+-ATPase in the gills and the digestive gland (DG) upon 4 d of exposure to 0.35 micro mol/L Cu2+. At day 7 of exposure to environmental Cu2+ concentrations total recoveries was observed in the kidneys and the gills for Ca2+-ATPase activity, and in the DG for Na+/K+-ATPase, but not at high doses. Ca and Na transport inhibition may entail disturbance of osmo-regulation and lead to continuous under-supply of Ca. Recoveries of Na+/K+-ATPase and Ca2+-ATPase enzymes function suggest that metal-detoxification is induced.&#13;
Phytochelatins (PC) are Cys-rich oligopeptides synthesised by phytochelatin synthase from glutathione in plants and fungi. Phytochelatin synthase genes have recently been identified in invertebrates; this allows us to hypothesize a role of PC in metal detoxification in animals.&#13;
In the second part of this work, PC and their precursors as well as metallothionein were analyzed in the gills and in the DG of Anodonta cygnea exposed to Cu2+. Our results showed for the first time the presence of PC2-4 in invertebrates. PC were detected in control mussels not exposed to metal, suggesting a role in essential metal homeostasis. Compared to control, PC2 induction was observed during the first 12 h of Cu2+ exposure. Those results confirm the role of PC as a first line detoxification mechanism in A. cygnea.&#13;
</description>
      <author>Olivier Santini</author>
      <category>doctoralthesis</category>
      <guid>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1138</guid>
      <pubDate>Fri, 12 Apr 2013 11:50:32 +0200</pubDate>
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      <title>Effektivität von Umweltbildung zum Thema Wasser – Empirische Studie zu Naturverbundenheit, Umwelteinstellungen und Umweltwissen</title>
      <link>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1127</link>
      <description>Die Stärkung des Umweltbewusstseins in der Bevölkerung ist heute notwendiger denn je. Um Umweltprobleme zu lösen und vorzubeugen, soll adäquate Umweltbildung unter anderem darauf abzielen, Motivation, Einstellungen und Wissen für den Schutz und Erhalt der natürlichen Umwelt zu fördern (IUCN, UNEP &amp; WWF, 1991; Potter, 2010). Naturverbundenheit stellt eine wichtige Motivation für den Umweltschutz dar und wird durch direktes, affektives Naturerleben gestärkt (z.B. Kaiser, Roczen &amp; Bogner, 2008; Davis, Green &amp; Reed, 2009). Diese Verbundenheit kann sich, ebenso wie Umwelteinstellungen, im Laufe des Lebens verändern, was sich wahrscheinlich auf die Effizienz von Umweltbildung bezüglich der unterschiedlichen Altersgruppen auswirkt (Bruni &amp; Schultz, 2010; Ernst &amp; Theimer, 2011). Frick und Kollegen (2004) gehen von drei kognitiven Wissensarten aus, die für ökologisch-nachhaltiges Handeln essentiell sind: System-, Handlungs- und Wirksamkeitswissen, welche bewusst in Bildungsaktionen integriert werden sollten. &#13;
Bis heute ist nicht genau untersucht, wie sich Schüler/innen ungleichen Alters hinsichtlich ihrer Naturverbundenheitswerte und Umwelteinstellungen unterscheiden. Es ist ebenfalls unklar, ob Kinder und vorpubertäre Jugendliche durch Umweltbildung in den genannten Aspekten unterschiedlich beeinflusst werden, und ob ein erzielter Effekt über einen längeren Zeitraum nach einer Intervention bestehen bleibt. Eine systematische Integration der drei Umweltwissensarten in ein Umweltbildungsprojekt stellt eine zusätzliche Herausforderung dar, durch die eine Zunahme der spezifischen Umweltwissensarten und deren Konvergenz nachgewiesen werden kann. Aus diesem Grund befasst sich die vorliegende Studie zunächst mit dem Ist-Zustand der Naturverbundenheit und den Umwelteinstellungen von 9 bis 13-Jährigen. Anschließend wird der Effekt eines umfassenden viertägigen Umweltbildungsprogramms auf Naturverbundenheit, Umwelteinstellungen und Umweltwissen untersucht. &#13;
Am Schullandheim-Projekt zum Thema „Wasser im Leben - Leben im Wasser“ nahmen rund 200 Schüler/innen teil. Die Naturverbundenheit wurde mit der INS-Skala ermittelt (Inclusion of Nature in Self; Schultz, 2002), die Umwelteinstellungen mit den Subskalen preservation und utilisation nach dem 2-MEV-Modell (Two Major Environmental Values; z.B. Bogner &amp; Wiseman 2006) und die Wissensarten mit drei neu entwickelten Skalen. Alle Skalen waren in einem Fragebogen eingebettet, welcher als Vor-, Nach- und Behaltenstest eingesetzt wurde. Eine externe Kontrollgruppe, die nicht am Projekt teilnahm, füllte ausschließlich die Fragebögen aus. &#13;
Die Ergebnisse zeigen für 9 bis 10-Jährige (Klasse 4) eine stärkere Naturverbundenheit und bessere Umwelteinstellungen als für 11 bis 13-Jährige (Klasse 6). Der Effekt des Umweltbildungsprojekts auf die Naturverbundenheit und Umwelteinstellungen ist bei den jüngeren Schüler/innen größer als bei den älteren. Beide Altersgruppen zeigen direkt nach der Teilnahme eine größere Naturverbundenheit, die jedoch nur bei den jüngeren Teilnehmer/innen auch über vier Wochen nach dem Projekt bestehen bleibt. Ein ähnliches Bild zeigt sich bezüglich der Umwelteinstellungen: Beide Einstellungen der jüngeren Schüler/innen verbessern sich durch die Programmteilnahme, jedoch bleibt nur preservation auch nach dem Projekt verbessert. Im Vergleich dazu zeigt die preservation-Einstellung der älteren Schüler/innen nur eine kurzfristige Verbesserung, die utilisation-Einstellung wurde nicht beeinflusst. Der Beginn der Pubertät bei den älteren Schüler/innen könnte der Grund für die geringere Naturverbun¬denheit und die ungünstigeren Umwelteinstellungen sein. Aufgrund ihres Alters streben die vorpubertären Schüler/innen wahrscheinlich bereits nach Unabhängigkeit und erleben emotionale Distanz zu anderen (Parra &amp; Oliva, 2009; Steinberg &amp; Silverberg, 1986) und möglicherweise auch zur Natur. Die neuen Skalen zur Messung der Umweltwissensarten erwiesen sich als reliabel und homogen. Das Umweltwissensniveau und die Wissenskonvergenz der Schüler/innen nehmen durch die Projektteilnahme zu und beide bleiben größtenteils über den Zeitraum von vier Wochen nach dem Projekt erhalten. Wirksamkeitswissen zeigt den geringsten Wissenszuwachs, was durch die hierarchische Abhängigkeit der Umweltwissensarten erklärt werden kann. Zusammenfassend war das viertägige Umweltbildungsprojekt bezüglich Naturverbundenheit, Umwelteinstellungen und Umweltwissen vor allem bei den 9 bis 10-jährigen Schüler/innen erfolgreich. Die Befunde werden abschließend bezüglich ihrer Herausforderungen für die Bildungsforschung und ihrer Konsequenzen für die schulische Umweltbildung beleuchtet. &#13;
</description>
      <author>Anne K. Liefländer</author>
      <category>doctoralthesis</category>
      <guid>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1127</guid>
      <pubDate>Wed, 27 Mar 2013 09:22:53 +0100</pubDate>
    </item>
    <item>
      <title>Light Harvesting using Metal-Organic and Organic Sensitizers in Hybrid Solar Cells: Synthesis, Characterisation and Application</title>
      <link>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1130</link>
      <description>This thesis addresses the question how to improve light harvesting with novel tailor-made metal-organic and organic sensitizers for solid-state hybrid solar cell applications. Two approaches are in the focus: 1) the design and synthesis of sensitizers featuring high extinction coefficients over a broad wavelength range and 2) modern device concepts to further enhance or extend the absorption by the combination of two sensitizers. In short: The primary goal was to broaden and boost the optical density of hybrid solar cells. To reach this, novel sensitizer with extended conjugated π-system providing excellent optical properties had to be designed and synthesised in complex multi-step reaction sequences. For ideal sensitizers, further aspects had to be taken into account such as structural demands, electronic properties, and the tendency towards aggregation.&#13;
The first part of this thesis deals with the synthesis, characterisation and application of a series of metal-organic ruthenium(II) donor-antenna complexes. In addition to the typically broad absorption of Ru(II)bis(bipyridyl)(NCS)2 complexes in the blue-green region arising from MLCT, these dyes feature much higher extinction coefficients in comparison to a commercially available reference dye lacking any donor-antenna groups. By the application of these Ru(II) complexes in solid-state dye-sensitized solar cells, we found a clear structure-property relationship. The performance - especially the photocurrent density - was significantly improved with increasing extension of the delocalized system of the donor-antenna groups.&#13;
To further boost the optical density in hybrid solar cells sensitized with a donor-antenna ruthenium dye (Ru-TPA-NCS), we developed an innovative and technically relevant concept for multichromophore sensitization involving a second sensitizer (TPD-dye). The latter absorbs in a region where Ru-TPA-NCS absorbs weakly. The solar cells were fabricated according to a novel method developed by us. However, the power conversion efficiencies of multichromophore hybrid blend solar cells were initially low due the weak interconnectivity of the TiO2 particles. This issue was addressed by an optimization of the TiO2:spiro-OMeTAD ratio and the addition of PCBM&#13;
A further concept dealing with the combination of two sensitizers in solid-state dye-sensitized solar cell was accomplished by co-sensitization of a triphenyldiamine-based dye (TPD-dye) absorbing in the blue region and squaraine dye (SQ-dye) mainly absorbing the red part of the visible spectrum. In this way, the optical response of the device was extended up to 700 nm. Under optimized conditions, a conversion efficiency of 2.41 % could be reached.&#13;
To accomplish the desired panchromaticity or even an extension of the absorption up to the NIR region with a single sensitizer, novel BODIPY dyes with excellent optical properties were designed and synthesised. We prepared BODIPYs with donor-groups to extend the delocalized system and integrated a meso-ethynyl bridge between the BODIPY core and the anchoring group to improve the electronic connection between them. For comparison, we synthesised the corresponding BODIPYs without donor-moieties and without ethynyl bridge. The multi-step synthetic routes were optimized, the mechanism of the donor-attachment was clarified and the introduction of the ethynylphenyl group in the meso-position was accomplished for the first time. The optical characterisation of the compounds disclosed an impressively broad and intensive spectral response, especially for a meso-ethynylphenyl BODIPY with donor-groups. This dye absorbs up to 1030 nm with high extinction coefficients. This makes suitable functionalised BODIPYs promising candidates for solar cell applications.&#13;
The next part took advantage of the excellent optical properties of BODIPYs and expanded the topic towards the concept of energy transfer. Here, an unattached energy donor dye provides additional adsorption and transfers the energy to a sensitizing acceptor dye. Indeed, for appropriate combinations an additional contribution to the external quantum efficiency was found in the absorption region of the energy donor dye.&#13;
Furthermore, a review chapter covering all aspects of dye-sensitized solar cells and the sensitizers is added as appendix.&#13;
In summary, this thesis presents the successful design, synthesis and characterisation of both metal-organic and organic sensitizers including ruthenium complexes, triphenyldiamine-based dyes, a squaraine sensitizer and BODIPY dyes. The sensitizers (either individually or in combination with complementary sensitizers) provide excellent optical properties for the application in solar cells. The applicability of these sensitizers was successfully demonstrated in standard solid-state dye-sensitized solar cells, in newly developed multichromophore hybrid blend solar cells, co-sensitized solar cells and in solid-state dye-sensitized solar cells taking advantage of energy transfer.&#13;
</description>
      <author>Katja Gräf</author>
      <category>doctoralthesis</category>
      <guid>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1130</guid>
      <pubDate>Tue, 26 Mar 2013 12:22:56 +0100</pubDate>
    </item>
    <item>
      <title>Über eine Erweiterung der Methode von Soshnikov zur Untersuchung des größten Eigenwerts auf unsymmetrische Verteilungen</title>
      <link>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1129</link>
      <description>Seit der Entdeckung des Halbkreisgesetzes durch Wigner werden reell-symmetrische Zufallsmatrix-Ensembles untersucht. Soshnikov hat in einer bahnbrechenden Arbeit gezeigt, dass für Wigner-Ensembles $A_n=(\xi_\ij)_{1\le i\le j\le n}$ mit symmetrisch verteilten Einträgen die Verteilung des größten Eigenwerts in einer geeigneten Skalierung für $n\to\infty$ universelles Verhalten zeigt und schwach gegen die Tracy-Widom-Verteilung, die Verteilung des Gauß'schen orthogonalen Ensembles, konvergiert. Für den Beweis nutzt Soshnikov die Momentenmethode. Hierbei wird die Analyse der Verteilungsfunktion des größten Eigenwerts auf die Analyse von Erwartungswerten von Spuren hoher Matrixpotenzen zurückgeführt (die Exponenten wachsen mit $n^{2/3}$). Die Spuren werden via $\tr A_n^{p_n}=\sum_{(i_0,\ldots,i_{p-1})\in[n]^p}\xi_{i_0,i_1}\xi_{i_1,i_2}\ldots\xi_{i_{p-1},i_0}$ als Summe über geschlossene Pfade kombinatorisch interpretiert. In der Analyse gilt es herauszufinden, welche Klassen von Pfaden (die mit den Momenten der Matrixeinträge in Verbindung stehen) die Spuren in der Asymptotik $n\to\infty$ dominieren. Es stellt sich heraus das dies Pfade sind, die jede ihrer Kanten genau zweimal durchlaufen. Das bedeutet, dass die Spuren asymptotisch nur  von den für alle Matrixeinträge gleichen zweiten Momenten abhängen, sie sind also asymptotisch für alle betrachteten Ensembles universell.&#13;
&#13;
Diese Methode wird in der vorliegenden Arbeit auf Wigner-Ensembles mit nicht notwendig symmetrischen Verteilungen der Einträge erweitert. Die Kombinatorik ist in diesem Fall komplexer. Resultat der Arbeit ist, dass die Methode von Soshnikov funktioniert, wenn folgende Bedingungen erfüllt sind: &#13;
&#13;
die ersten und dritten Momente der Einträge sind~0&#13;
&#13;
für die 97.\ Momente existiert eine in~$n$ gleichmäßige Schranke.</description>
      <author>Felix Grimme</author>
      <category>doctoralthesis</category>
      <guid>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1129</guid>
      <pubDate>Mon, 25 Mar 2013 11:11:34 +0100</pubDate>
    </item>
    <item>
      <title>Heterogeneous chemistry of HONO and surface exchange</title>
      <link>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1125</link>
      <description>Nitrous acid (HONO) is an important precursor of OH radicals, which are the key oxidizing species in the atmosphere and are therefore called the detergent of the atmosphere. Despite the importance of HONO for atmospheric chemistry and about 30 years of detailed research the exact formation mechanisms of both day- and night-time formation remain unclear. The main formation pathways discussed to date are heterogeneous reactions with nitrogen dioxide as the HONO precursor or microbiological activity in soil. As the ground surface is a major source of HONO, the vertical distribution of HONO is very sensitive to the extent of vertical mixing. Additionally, some uncertainty in comparing laboratory and field measurements might be caused by the not yet clarified role of relative humidity and surface wetness on HONO formation and deposition, respectively. These influences have been investigated in field measurements in the present study. For HONO measurements, LOng Path Absorption Photometers (LOPAPs) have been deployed.&#13;
During the Diel Oxidant Mechanism In relation to Nitrogen Oxides (DOMINO) campaign, HONO and other reactive trace gases were measured above a pine forest in south west Spain. In line with all recently published work, this study also found a substantial daytime formation of HONO. This so-called additional daytime source or unknown source was found to be slightly correlated (r² = 0.16) with actinic flux. Normalizing this unknown source to nitrogen dioxide mixing ratios improved the correlation (r² = 0.38), which indicates an influence of nitrogen dioxide availability. The coefficient of determination improved further to 0.47 by restricting the data to clear days and rejecting data from advection events. Thus, a fraction of the unknown source might be explained by light-induced nitrogen dioxide conversion but other factors have to be taken into account. Two processes of light-induced nitrogen dioxide conversion, proposed by recent laboratory studies, were shown to be negligible for the semirural conditions during our study. HONO photolysis was found to be the most important primary OH-radical source during DOMINO, contributing 20 % more OH than ozone photolysis integrated over the day. &#13;
Vertical exchange of HONO was studied at the “Waldstein-Weidenbrunnen” field site of the University of Bayreuth in the Fichtelgebirge Mountains in south east Germany. The simultaneous HONO measurements in and above a forest canopy highlighted the importance of turbulent exchange for the vertical distribution of HONO mixing ratios. The so-called coupling regimes of the forest (with the air layers above) were found to be a very useful micrometeorological concept to study vertical differences of mixing ratios in a forest. They denote which parts of the forest are coupled to the air layer above the canopy and thus take part in turbulent exchange of energy and matter. With this coupling tool it was possible to explain vertical mixing ratio differences by different sources and sinks and the magnitude of the difference by the intensity of vertical exchange. Studying the vertical mixing ratio differences of HONO, an unexpected result was that during late morning and around noon they were close to zero. As the lifetime of HONO below canopy of about 250 to 300 min was a factor of 25 to 30 longer than that above canopy of about 10 min, large mixing ratio differences would have been expected. The lack of these differences could be explained by efficient vertical mixing, which was indicated by a full coupling of the forest or a coupling by sweeps and only intermittent decoupling of the subcanopy during these periods. Around sunset, the whole forest became decoupled from the air layers above. This caused a steep increase in mixing ratio differences up to about 170 ppt due to a faster increase below canopy, indicating local formation below the canopy. &#13;
HONO and RH are correlated due to their diurnal cycles which are mainly caused by radiation. This diurnal contribution has to be removed from the respective signals in order to extract correlations on other timescales. Singular System Analysis, a tool for time series analysis, has been applied successfully to remove diurnal variations and long-term trends from the HONO and RH time series. Correlations of the higher frequency contributions of the remaining signals were poor but slightly positive. The HONO mixing ratios increase exponentially with RH from about 25 % RH to about 70 % RH. No clear correlation was found between around 70 and 95 % RH. Above 95 % RH, HONO mixing ratios decreased due to HONO uptake in droplets and liquid films. These features are in line with previously proposed mechanisms for interactions of water and HONO on surfaces.&#13;
The study highlighted the need to assess turbulent transport and surface properties in addition to chemistry for understanding the heterogeneous reactions and processes forming HONO.&#13;
</description>
      <author>Matthias Sörgel</author>
      <category>doctoralthesis</category>
      <guid>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1125</guid>
      <pubDate>Fri, 22 Mar 2013 10:48:27 +0100</pubDate>
    </item>
    <item>
      <title>Integrated size and price optimization for a fashion retailer</title>
      <link>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1124</link>
      <description>This thesis is the result of a collaboration with a German fashion retailer which lasted&#13;
for several years. The aim was the development of a decision-support system for the&#13;
supply of the about 1300 branches in Germany.&#13;
&#13;
There are some specialties about the situation at our industrial partner: The branches&#13;
are supplied by prepackaged size-assortments of a product which we call lot-types.&#13;
With the objective to economize handling cost, these lot-types are already composed&#13;
at the respective low-wage country where the article is also produced. The expense at&#13;
the German central warehouse is further reduced by allowing only four or five different lot-types for the delivery of one product. Moreover, each branch is supplied by a&#13;
certain quantity of a single lot-type.&#13;
&#13;
For the most fashion articles replenishment is not possible. The sales success of&#13;
a product is a priori unknown. Historical sales data can only be used on a higher&#13;
aggregation level, e.g., the average historical demand on the commodity group level.&#13;
Demand estimation is therefore very vague. Under- and oversupplies are unavoidable.&#13;
Influence over the sales process is possible by marking down prices. To compensate&#13;
for an oversupply of a product, weekly the price can be reduced to predefined price&#13;
steps which depend on the starting price of the product. Mark-downs for an article are&#13;
performed simultaneously for all branches and sizes.&#13;
&#13;
Within the cooperation mathematical problem formulations with the aim to minimize measures for the deviation of supply from estimated demand had been developed.&#13;
In these measures the selling process is not or only very vaguely regarded.&#13;
&#13;
Now we include the possibility of marking down prices during the selling time&#13;
already when deciding on the supply. The result is the two-stage stochastic program&#13;
ISPO: The so-called first stage decision is the determination of a supply policy. The&#13;
second stage decision, or recourse, is the decision on mark-downs during the selling&#13;
time. ISPO yields an expected revenue maximizing supply strategy and corresponding&#13;
optimal mark-down strategies for the considered scenarios.&#13;
&#13;
ISPO it too complex to solve it via standard approaches. Customized methods had&#13;
to be devised to solve ISPO. On the one side we present an exact solver for benchmarking. On the other side a fast heuristic was developed for practical use at our partner.&#13;
The basic idea of our exact solver is to enumerate all possible mark-down strategies.&#13;
With this it is possible to reduce ISPO to a former formulation for the optimization of&#13;
supply, which can be solved via standard approaches.&#13;
&#13;
In practice enumeration of all valid mark-down strategies for the purpose of solving&#13;
ISPO is for reasons of time impossible. Therefore the idea is extended to a customized&#13;
Branch&amp;Bound approach. In this context we derived dual bounds for general two-stage stochastic programs which are based on the so-called wait-and-see solution from&#13;
stochastic programming. We show that in general our bounds are tighter.&#13;
&#13;
The heuristic, beginning with a valid second stage decision, determines an optimal&#13;
first stage decision and alternates between solving the first stage and the second stage&#13;
until convergence is reached. The optimality gap is small enough to justify a practical&#13;
use at the industrial partner.&#13;
&#13;
In practice the by ISPO proposed mark-down strategies are not applied; instead&#13;
latest sales figures are exploited. According to these and an updated demand estimation&#13;
weekly a new optimal mark-down strategy for the remaining selling time of the product&#13;
is determined. For this purpose we propose an algorithm which relies on dynamic&#13;
programming and tries to exclude non-optimal solutions a priori by dominance checks.&#13;
&#13;
ISPO, more precisely our heuristic approach, together with the weekly adaption of&#13;
the mark-down strategy forms our decision support system for integrated size and price&#13;
optimization DISPO.&#13;
&#13;
We tested DISPO in a five-month field study, performed as a statistical experiment,&#13;
at our partner where pairs of similar branches were compared. At one branch of each&#13;
pair, the test branch, supply and mark-down decisions came from ISPO. With respect&#13;
to latest sales figures the mark-down decisions were weekly updated via our dynamic&#13;
programming approach. At the other branch, the control branch, these decisions were&#13;
not integrated: Supply was determined according to a strategy resulting from a former&#13;
model that disregarded the selling process and mark-downs were handled manually by&#13;
our partner. For the branches at which the decisions of ISPO were implemented an&#13;
average raise of 1.5 percentage points of relative revenue was observed.</description>
      <author>Miriam Kießling</author>
      <category>doctoralthesis</category>
      <guid>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1124</guid>
      <pubDate>Fri, 22 Mar 2013 10:23:35 +0100</pubDate>
    </item>
    <item>
      <title>THE INDEX THEOREM FOR QUASI-TORI</title>
      <link>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1102</link>
      <description>The Index theorem for holomorphic line bundles on complex tori&#13;
asserts that some cohomology groups of a line bundle vanish according&#13;
to the numbers of negative and positive eigenvalues of the associated&#13;
hermitian form. In this thesis, this theorem is generalized to quasi-tori,&#13;
i.e. connected complex abelian Lie groups which are not necessarily&#13;
compact. In view of the Remmert–Morimoto decomposition of&#13;
quasi-tori as well as the Künneth formula, it suffices to consider only&#13;
Cousin-quasi-tori, i.e. quasi-tori which have no non-constant holomorphic&#13;
functions. The Index theorem is generalized to holomorphic line&#13;
bundles, both linearizable and non-linearizable, on Cousin-quasi-tori&#13;
using L2-methods coupled with the Kazama–Dolbeault isomorphism&#13;
and Bochner–Kodaira formulas.</description>
      <author>Tsz On Mario Chan</author>
      <category>doctoralthesis</category>
      <guid>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1102</guid>
      <pubDate>Fri, 01 Mar 2013 10:43:10 +0100</pubDate>
    </item>
    <item>
      <title>Structural analysis of nanoparticles by small angles X-ray scattering</title>
      <link>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1095</link>
      <description>The objective of this work was to analyze nano-scaled particles by the combination of small angle x-ray scattering (SAXS), electron microscopy (TEM and cryo-TEM) and dynamic light scattering (DLS). Two systems with totally di_erent morphologies and compositions have been investigated: spherical particles of calcium-phosphate-protein complexes and hamburgers of semi-crystalline polybutadiene/polyethylene nanoparticles.&#13;
The study of the calcium-phosphate-protein complexes consisted in looking for the influence of a protein, Fetuin-A, also called ahsg, onto the calci_cation at early stage. For the purpose, calcium and phosphate ions were mixed with or without the presence of Fetuin-A in a buffr solution of pH=7.4. In a first step, DLS measurements were realized to better appreciate the effect of the total weight percentage of Ca2+ and PO43- ions. These experiments, withtout addition of ahsg, demonstrated that for a lower weight fraction, the particles formed are smaller. Studies with addition of Fetuin-A affected the calcification during the first minute of this process. The early formation of calcium phosphate complexes has been successfully followed by TR-SAXS. A very fast nucleation of nanoparticles within 1 second has been detected. For the first time, the role of the glycoprotein Fetuin-A at the very early stage of calcification has been qualitatively highlighted: ahsg inhibits the aggregation of calcium phosphate particles. Thus, Fetuin-A plays an important role in the fetal serum in the pre-formation of the skeleton of Vertebrates. This study demonstrated that a physiological concentration of this glycoprotein (15 µM) is suffcient to completely inhibit the aggregation of calcium phosphate particles.&#13;
&#13;
Freely suspended nanoparticles of syndiotactic polybutadiene have been studied. By using the combination of cryo-TEM and SAXS, it has been shown that they consist of remarkably thin polymer crystalline lamella. Different models have been compared in order to theoretically fit the experimental SAXS data: homogeneous and heterogeneous (two and three different electron densities within one particle) nanoparticles. The presence of amorphous and crystalline polybutadiene has been demonstrated by the X-ray diffraction. The necessity of using an additional layer of SDS for the modeling is explained by the abundancy of SDS added after the synthesis of the polybutadiene particles (weight ratio ca. 1:1) and by the modeling of the SAXS theoretical intensities which were not sufficient without taking into account the presence of SDS. After the formation of semi-crystalline nanoparticles of PE, these new nanoparticles open a new route to the synthesis of nanopolymers of interesting physico-chemical properties such as semi-conductors or photovoltaic compounds. &#13;
&#13;
Finally, in contrast to recent literature on bulk polyethylene (PE), this thesis investigated freely suspended nanoparticles of PE. As suggested by Weber and coworkers, the combination of SAXS and cryo-TEM has been used for this study. The structure of individual PE nanocrystals has been determined in detail and an improved model of the form factor (SAXS) has been developped in close collaboration with Priv.-Doz. Dr. Ludger Harnau. The second part of this thesis mainly deals with the annealing of these PE particles. For the first time, it is shown that the effect of the annealing process results in a doubling of the crystalline layer of the PE nanoparticles. This behaviour could be traced back to the unlooping of the PE chains. In addition, a linear relationship between the reciprocal of the crystalline layer and the annealing temperature has been experimentally drawn. This line was predicted by the Gibbs-Thomson equation according to the literature. This result is important because it allows controlling the crystalline thickness and physical properties of the system, by the temperature.&#13;
</description>
      <author>Christophe N. Rochette</author>
      <category>doctoralthesis</category>
      <guid>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1095</guid>
      <pubDate>Wed, 27 Feb 2013 12:55:02 +0100</pubDate>
    </item>
    <item>
      <title>Soil erosion and conservation potential of row crop farming in mountainous landscapes of South Korea</title>
      <link>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1100</link>
      <description>Soils play an essential role for mankind because they provide fundamental ecosystem services required for human life, primarily for the production of food by providing the environment for plant growth. However, soils worldwide became highly threatened by human induced degradation, especially as a consequence of accelerated erosion by water during recent decades. In consideration of climate change and an increasing food demand of a rising population, there is an urgent need to conserve the soil resources by implementing effective erosion control measures for agricultural production. The effective implementation of those measures strongly depends on the specific conditions of particular regions and requires the analysis of the existing farming systems and their capability for erosion control.&#13;
Objective of this thesis is the analysis of the major agricultural practices applied for row crop cultivation in mountainous watersheds of South Korea with respect to water erosion and the identification of their conservation potential. Our first two studies analyze the subsurface flow processes, the runoff patterns, and the associated erosion rates of the widely applied plastic covered ridge-furrow system (plastic mulch), and our third study investigates the impact of herbicide applications on erosion associated with conventional and organic farming. To analyze the flow processes induced by the plastic mulch cultivation, we conducted four irrigation experiments on potato fields that represent a smooth surface, uncovered ridges, and plastic covered ridges with and without a developed crop canopy. With an automatic sprinkler, we irrigated small plots with a dye tracer solution of Brilliant Blue and potassium iodide, collected surface runoff, and excavated soil profiles to visualize the subsurface flow patterns, which were subsequently analyzed by image index functions. We found that the ridge-furrow system, especially when ridges are covered with plastic, decreased infiltration and generated high amounts of surface runoff, whereas a developed crop canopy increased infiltration due to interception and stem flow. The analyses of the subsurface flow patterns show that the plastic covered ridge-furrow system induces preferential infiltration in furrows and planting holes due to its topography and the impermeable covers, but that the impact on flow processes in the soils is relatively small compared to the impact on runoff generation. To identify the patterns of overland flow and the erosion rates associated with the plastic mulch system, we installed runoff collectors to monitor runoff and sediment transport of two potato fields with concave and convex topographies, and we applied the EROSION 3D model to compare the plastic covered ridge-furrow system to uncovered ridges and a smooth surface. We found that plastic mulch cultivation considerably increases soil erosion compared to uncovered ridges as a consequence of high amounts of surface runoff. Our results show that the ridge-furrow system concentrated overland flow on the concave field, resulting in severe gully erosion, but prevented flow accumulation and reduced erosion on the convex field, which demonstrates that the effect of this cultivation strategy is primarily controlled by the field topography and its orientation. To analyze the effects of conventional and organic farming on water erosion, we measured multiple vegetation parameters of crops and weeds of conventional and organic farms cultivating bean, potato, radish, and cabbage, and we simulated long-term soil loss rates with the Revised Universal Soil Loss Equation (RUSLE). We found that organic farming reduced erosion for radish, as a result of an increased weed biomass due to the absence of herbicides, but that it increased erosion for potato due to lower crop coverage, presumably as a consequence of crop-weed competition or herbivory associated with the absence of agricultural chemicals. Although we demonstrated that a developed weed cover in the furrows can potentially decrease the erosion risk for row crops, our results show that the average annual erosion rates of both farming systems exceed by far any tolerable soil loss.&#13;
In consideration of the generally high soil loss found in our studies, we conclude that the applied farming practices are not capable for effective erosion control and soil conservation in this region. However, based on our findings, we could identify possible modifications of those practices that can help to reduce the risk of erosion in the future. We recommend perforated plastic covers for ridges to reduce runoff generation, and the orientation of the ridge-furrow system along the contours or towards field edges to prevent flow accumulation and gully formation. Additionally, we suggest residue mulching of furrows to protect the soil surface from overland flow, and the cultivation of winter cover crops after harvest to maintain a better soil cover throughout the year.&#13;
</description>
      <author>Sebastian Arnhold</author>
      <category>doctoralthesis</category>
      <guid>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1100</guid>
      <pubDate>Tue, 26 Feb 2013 11:25:23 +0100</pubDate>
    </item>
    <item>
      <title>Flow and transport processes as affected by tillage management under monsoonal conditions in South Korea</title>
      <link>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1099</link>
      <description>A sustainable agriculture, which provides enough yields to satisfy the food demand and minimizes the impacts on ecosystem services such as provision of high water quality, is challenging especially in monsoon regions. In this thesis, plastic mulched ridge cultivation (RTpm) under monsoonal conditions and its impact on flow processes and nitrate transport was investigated.&#13;
 &#13;
On hillslopes, we monitored surface and subsurface flow processes in four plastic mulched potato fields using a network of tensiometers, FDR sensors, runoff collectors and flow dividers as well as Brilliant Blue FCF tracer experiments. The obtained datasets were used to calibrate the process-based models HYDRUS 2/3D and EROSION 3D in order to quantify drainage water fluxes, surface runoff and erosion rates of RTpm compared to ridge tillage without coverage (RT) and conventional flat tillage (CT). In a flat terrain, N fate under fertilizer rates at 50, 150, 250 and 350 kg NO3− ha−1 was investigated in a plastic mulched radish field using suction lysimeters, tensiometers and a 15N tracer experiment. We used datasets of nitrate concentrations and matric potentials to calibrate a water flow and solute transport model using the numerical code HydroGeoSphere.&#13;
&#13;
RTpm affects soil water dynamics dominantly during dry periods, when ridge soil was drier compared to furrow soil caused by the protective plastic coverage and root water uptake in ridges. Hence, pressure head gradients induced lateral flow from furrows to ridges. Under monsoonal conditions, soil was fully saturated and down slope lateral flow occurred in the coarse textured topsoil. The dye tracer experiments showed that matrix flow dominated in the sandy topsoil. Lateral funnel flow above the tillage pan was the prominent preferential flow path. Unexpectedly, macropore flow in deeper soil horizons was not detected. The field and modeling studies revealed that surface runoff was substantially increased under RTpm compared to RT and CT. However, the field topography primarily controlled surface runoff and erosion rates. The concavity of the field led to flow accumulation and high erosion losses in the center of the field, while a convex shape resulted in less soil erosion. &#13;
&#13;
NO3− leaching was found to be the prominent pathway especially during the early season. Furthermore, the biomass production did not significantly differ between NO3− fertilizer rates of 150 to 350 kg ha−1. Hence, we recommend NO3− fertilizer application of 150 kg ha−1, a better fertilizer placement and split applications. We simulated whether the given recommendations on fertilizer best management practices (FBMPs) decreased NO3− leaching amounts. Compared to RT under conventional fertilization in ridges and furrows, the simulations showed that NO3− leaching can be considerably reduced up to 82% by combining RTpm, fertilizer placement only in ridges and split applications with a total fertilizer NO3− amount of 150 kg ha−1.&#13;
&#13;
Based on these findings, the impact of RTpm on flow and transport processes has to be evaluated differently depending on terrain complexity. In a flat terrain, where surface runoff processes are absent or minimal, RTpm has several advantages. Beside functions such as weed control, and earlier plant emergence due to higher temperatures, plastic mulching decreases drainage water and NO3− leaching. Thus, RTpm enhances nutrient retention below the plastic mulch and reduces NO3− groundwater contamination risk. On slopes, where precipitation contributes substantially to surface runoff, RTpm even increases runoff, soil erosion and surface leaching of agrochemicals into aquatic systems. &#13;
&#13;
This thesis provides several recommendations, aiming to minimize environmental impacts and to decrease costs of fertilizer and herbicide inputs. To reduce surface runoff and soil erosion at sloped fields, we suggest applying perforated plastic mulch and a ridge configuration following contours of the field. Furthermore, we recommend omitting application of herbicides in furrows to allow weed growth, which slows down runoff processes. These suggestions would increase infiltration and subsurface flow processes automatically become more important. However, absent preferential flow to deeper soil layers indicated a low groundwater contamination risk. Since funnel flow above the tillage pan was found to be the most important preferential flow path, we propose the establishment of riparian buffer zones. This would also help to reduce the discharge of sediments and fertilizers via surface runoff into the streams. Finally, FBMPs such as fertilizer placement only in ridges and split applications were found to decrease nitrate leaching considerably. Hence, we suggest applying FBMPs with impermeable plastic mulch in flat terrain, while on hill slopes FBMPs should be applied with perforated plastic mulch. To reduce the leaching and erosion risk after harvest when the plastic mulched ridges are removed, we recommend cultivating cover crops. &#13;
</description>
      <author>Marianne Ruidisch</author>
      <category>doctoralthesis</category>
      <guid>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1099</guid>
      <pubDate>Tue, 26 Feb 2013 10:58:13 +0100</pubDate>
    </item>
    <item>
      <title>Sozialphilosophie und Geldpolitik bei Friedrich August von Hayek, Walter Eucken, Joseph Alois Schumpeter, Milton Friedman und John Maynard Keynes</title>
      <link>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1090</link>
      <description>Die globale Finanzkrise, die im Frühjahr 2007 begann und im September 2008 durch den&#13;
Zusammenbruch der Investmentbank Lehman Brothers eskalierte, begann im vierten Quartal&#13;
2008 weltweit auf die Realwirtschaft durchzuschlagen. Die deutsche Bundesregierung&#13;
rechnete damit, dass im Jahr 2009 das Bruttoinlandsprodukt (BIP) um 6 Prozent einbrechen&#13;
werde – so stark wie nie seit dem Zweiten Weltkrieg. Es kam mit einem BIP-Rückgang von&#13;
4,9 Prozent dann zwar nicht ganz so schlimm, aber auch diese Rezession war die stärkste&#13;
seit 1945. Für diese dramatischen Entwicklungen lieferten Ökonomen im Wesentlichen zwei&#13;
Erklärungsmuster: Die einen gaben den Zentralbanken die Schuld, sie hätten in den zwei&#13;
Jahrzehnten vor der Krise zu viel Liquidität geschaffen, die dann zu Preisblasen etwa auf&#13;
dem amerikanischen Immobilienmarkt führte. Andere machten eine zu schlaffe Regulierung&#13;
und die Liberalisierung der Finanzmärkte für die Entwicklungen verantwortlich.&#13;
Vor dem Hintergrund dieser Ereignisse entstand die Idee, nicht nur eine technische Analyse&#13;
durchzuführen um zu erkennen, welches Erklärungsmuster plausibler sei. Stattdessen sollte&#13;
analysiert werden, wie sich diese diametral wiedersprechenden Aussagen von Ökonomen&#13;
ideengeschichtlich erklären lassen. Es erschien nötig, sich ideengeschichtlich mit&#13;
Sozialphilosophie, der Rolle des Staates in der Wirtschaft sowie dem Wesen des Geldes und&#13;
des Zinses in den wichtigsten ökonomischen Schriften des 20. Jahrhunderts zu&#13;
beschäftigen. Dabei sollte es um die Frage gehen, ob bei Ökonomen und Sozialphilosophen&#13;
zwischen den generellen gesellschafts- und wirtschaftspolitischen Vorstellungen einerseits&#13;
und den geldpolitischen Vorstellungen andererseits ein Zusammenhang besteht. Diese&#13;
Frage sollte durch einen Literaturvergleich verschiedener Staats- und Geldtheoretiker geklärt&#13;
werden, die – bei allen Unterschieden im Detail – für sich das Attribut „liberal“ reklamieren.&#13;
Die vorliegende Arbeit analysiert folglich die Werke von fünf großen Wirtschafts- und&#13;
Sozialphilosophen, nämlich von Friedrich August von Hayek als Repräsentant der&#13;
Österreichischen Schule der Nationalökonomie, Walter Eucken als Vertreter der Freiburger&#13;
Schule der Ordnungsökonomik, Joseph A. Schumpeter als Vertreter einer&#13;
Unternehmertheorie, Milton Friedman als Begründer des Monetarismus und John Maynard&#13;
Keynes als Vertreter einer expansiven Geld- und Fiskalpolitik. Dabei wird ein&#13;
Zusammenhang des Denkens in Bezug auf allgemeine staatsphilosophische Vorstellungen,&#13;
wirtschaftspolitische Ziele und die Aufgabe sowie den Instrumentenkasten der Geldpolitik&#13;
hergestellt.&#13;
Dabei zeigt sich: Individualistische Vorstellungen über die Gesellschaft gehen mit&#13;
Präferenzen für eine geringe Tätigkeit des Staates in der Wirtschaft sowie einer&#13;
weitgehenden, teils sogar völligen Entkopplung der Geldpolitik von politischer Einflussnahme&#13;
einher. Umgekehrt gehen Vorstellungen, die weniger einem negativen als einem positiven&#13;
Freiheitsbegriff folgen und dem wirtschaftlichen Erfolg des Kollektivs den Vorzug vor der&#13;
Freiheit des Einzelnen geben, mit einer stärkeren Rolle des Staates im wirtschaftlichen&#13;
Koordinations- und Allokationsprozess einher und fordern zugleich eine aktive Rolle der&#13;
Geldpolitik bei der Steuerung des wirtschaftlichen Prozesses. Daraus ist wiederum zu&#13;
schließen: Die Forderung nach einer expansiv ausgerichteten Geldpolitik zur Stimulierung&#13;
von Konjunktur und Wachstum beruht ideengeschichtlich nicht nur auf technischen&#13;
Überlegungen zur Effizienz, sondern stammt von einer grundsätzlich kollektivistischer – teils&#13;
sozialistischer – ausgerichteten Grundüberzeugung. Die Argumentation zum Beispiel für&#13;
oder gegen eine konjunkturstützende Geldpolitik leitet sich nicht nur aus theoretischen&#13;
ökonomischen Modellen ab, deren Richtigkeit etwa durch empirische Methoden überprüft&#13;
werden kann. Sie leitet sich auch aus grundsätzlichen Überzeugungen zum Beispiel über&#13;
den Wert der individuellen Freiheit oder des Schutzes von Eigentumsrechten ab. In der&#13;
politischen wie in der wissenschaftlich-ökonomischen Diskussion kommt dieser Aspekt&#13;
allerdings zu kurz.</description>
      <author>Stephan Balling</author>
      <category>doctoralthesis</category>
      <guid>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1090</guid>
      <pubDate>Mon, 25 Feb 2013 15:45:25 +0100</pubDate>
    </item>
    <item>
      <title>The origins of olivine fabric transitions and their effects on seismic anisotropy in the upper mantle</title>
      <link>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1063</link>
      <description>Convecting mantle plays a central role in the thermal and geochemical evolution of the Earth. It provides the principal force responsible for major geological features such as mountains and ocean basins. Plate tectonics and its violent consequences such as earthquakes and volcanoes are all manifestations of the dynamics of the convective mantle. Shearing forces generated by mantle convection leads to lattice preferred orientation (LPO) of the major upper mantle mineral phases. LPO that develops in this way is thought to be the principal cause behind seismic anisotropy in the upper mantle, which can consequently be used to chart convective flow of the mantle.&#13;
Strong changes in seismic anisotropy occur in the top 300 km of the upper mantle where olivine is the principal mineral. In this study a solid media high pressure deformation apparatus, called the deformation-DIA or D-DIA, has been used to deform aggregates of San Carlos olivine in simple shear geometry at pressures between 3 and 8.5 GPa and temperatures from 1300-1500°C. As part of this project a high pressure and temperature solid-media cubic assembly was developed to facilitate these experiment that employed alumina pistons cut at 45° to shear the sample but minimized cold deformation of the sample by employing initially porous alumina in the sample column. Once stable high pressures and temperature were reached the cubic assembly was deformed by compressing two vertically oriented anvils of the D-DIA, while the four horizontally oriented anvils were maintained at a constant loading force. This assembly shortening led to shearing of the olivine sample. Recovered samples were analyzed for fabric development employing electron backscattered diffraction (EBSD) and microstructure was observed using transmission electron microscopy (TEM).&#13;
Experiments were performed at each pressure and temperature as a function of strain rate and H2O content. In dry olivine deformation experiments performed at slower strain rates an A-type fabric dominated at all pressures and temperatures, implying deformation by dislocation glide through the (010)[100] slip system. At higher strain rates evidence for the B-type fabric was observed, suggesting increased activity of the (010)[001] slip system at higher stresses. Recrystallization grains size and dislocation densities were used to estimate stresses in the samples and a good correlation was observed between strain rate and estimated flow stresses. Dry experiments from 8.5 GPa and 1500°C exhibited no LPO, which may be an indication for deformation through diffusion accommodated grain boundary sliding at these conditions. No indication was found that pressure influences the dominant slip system in olivine, in contrast to previous studies. It is considered that previously reported incidences of pressure effects can in fact be attributed to the development of higher stresses in experiments performed at higher pressures.&#13;
Fabrics in H2O bearing olivine deformed at similar conditions revealed the overriding dominance of the C-type fabric, developed through action of the (100)[001] slip system. Variations in pressure, temperature and strain rate had little influence on this fabric development. TEM observations confirmed the presence of dislocations with slip systems consistent with the development of the macroscopic fabrics. Viscoplastic self consistent modeling was employed to understand the development of fabric in the samples and to estimate the relative contributions of variations slip systems to the developed fabrics. &#13;
These results are used to construct an olivine fabric map which is found to be consistent with some previous studies at lower pressures. It is argued that the decrease in seismic anisotropy observed in the top 300 km of the upper mantle cannot originate from a pressure induced change in the dominant olivine deformation fabric. Instead it is argued that changes in the H2O content of olivine with depth cause a shift in the dominant fabric from A-type to C-type, with a possible excursion through the E-type fabric, dominant slip system (001)[100], which was, however, not observed in this study. Modeling is used to show that this variation in fabric with depth can cause the observed weakening the seismic anisotropy in the upper mantle if the olivine H2O content increases from below 100 ppm at 50 km to 250 ppm at 300 km. Rather than implying an increased in the H2O content of the mantle with depth, however, it is argued that this change in olivine H2O content can be caused by changes in the H2O olivine-pyroxene partition coefficients with depth, for a fixed bulk mantle H2O content of 200 ppm.&#13;
Similar deformation experiments performed on a peridotite assemblage at 8.5 GPa and 1300°C indicate identical olivine fabrics to those observed in monomineralic experiments at the same conditions. Fabrics for diopside and enstatite were found to be similar to those found in previously performed lower pressure experiments.&#13;
Experiments on a piezoelectric single crystal of GaPO4 were performed in the D-DIA and 6-ram MAVO press at high pressures in order to measure charge on the crystal developed through the application of deviatoric stresses. Electrical charges were measured through the use of an operational amplifier. Experiments performed at room temperature using a developed cubic assembly were successful in measuring quantifiable electrical charges resulting from the advancement of the deformation anvils by as little as 0.5 µm. Although the piezoelectric constant for this material is not yet calibrated at high pressures, stresses were estimated from the measured charges and measureable values were in the range 4-350 MPa.</description>
      <author>Sushant Shekhar</author>
      <category>doctoralthesis</category>
      <guid>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1063</guid>
      <pubDate>Thu, 21 Feb 2013 12:20:22 +0100</pubDate>
    </item>
    <item>
      <title>Kinetische Untersuchungen der Halogen-Aktivierung einer simulierten Salzpfanne in einer Smogkammer    </title>
      <link>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1086</link>
      <description>Reaktive Halogenverbindungen, insbesondere solche von Br und Cl, spielen eine wichtige Rolle beim atmosphärischen Abbau von Ozon und Kohlenwasserstoffen. Auch beeinflussen sie die Radikalzusammensetzung in der Troposphäre und haben somit eine Auswirkung auf klimarelevante Prozesse. Ziel dieser Arbeit war die Untersuchung der Halogenfreisetzung aus einer künstlichen Salzpfanne bei unterschiedlichen umweltrelevanten Bedingungen, wie relative Feuchte (RF) und Konzentrationen von Stickoxiden und Kohlenwasserstoffen, in einer Smogkammer. Diese Methode wurde in Rahmen  dieser Arbeit entwickelt, um diese bislang wenig untersuchte Quelle von Halogenen zu untersuchen.  Als Modell für die Salzpfanne wurde eine umweltrelevante Mischung von NaCl mit NaBr verwendet. Kinetische Berechnungen lieferten die zeitlichen Verläufe der Cl-Atome und OH-Radikale aus dem Verbrauch der zugesetzten Kohlenwasserstoffe und der Br-Atome aus dem Ozonverbrauch und UV-Absorptionsmessungen die Verläufe der BrO-Radikale. Während  Salzpfannen-Experimenten bei einer mittleren RF  von 37 %  erreichte  die Cl-Konzentration ein Maximum von 5 x104 cm-3. Ein rascherer Ozonabbau wurde bei größerer RF und zugleich höherer BrO-Konzentration beobachtet. Bei den Experimenten in Anwesenheit von sekundären organischen Aerosolen (SOA)  verlangsamte sich der Ozonabbau um einen Faktor 16. Das BrO-Mischungsverhältnis erreichte in diesem Fall maximal 0.15 ppb im Vergleich zu Experimenten ohne SOA, bei denen das BrO Mischungsverhältnis 6 ppb erreichte. Nach Einwirkung der aus der Salzpfanne freigesetzten Halogene auf das SOA wurde ein erneutes Partikelwachstum beobachtet. Dies könnte eine Hauptsenke für Halogene in der Atmosphäre darstellen und einen neuen Weg zur Partikelbildung.&#13;
&#13;
</description>
      <author>Natalja Balzer</author>
      <category>doctoralthesis</category>
      <guid>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1086</guid>
      <pubDate>Fri, 15 Feb 2013 12:02:07 +0100</pubDate>
    </item>
    <item>
      <title>Rhizodeposition and its effects on C fluxes in the soil</title>
      <link>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1066</link>
      <description>Organic compounds released from living roots (rhizodeposits) are easily available sources of energy for microorganisms strongly affecting soil organic matter (SOM) dynamics. Although, rhizodeposition is a key driver of microbially mediated processes in the soils, it still remains the most uncertain component of the terrestrial carbon (C) cycle. &#13;
The input of C through rhizodeposition occurs in temporal and spatial hotspots. The objective of Study 1 was to determine the dynamics of hotspots of recently assimilated C in ryegrass roots. Shoots were 14CO2 pulse labeled and the allocation patterns at increasing time intervals were visualized by phosphor imaging. We could show a quick translocation of assimilated C to the roots. 14C hotspots were detected at the root tips already 6 hours after labeling. The hotspots remained active for at least 2 days. Eleven days after assimilation the hotspots at the tips had disappeared, and the 14C distribution was much more even than after 6 hours and 2 days. &#13;
Through the availability of rhizodeposits, hotspots create preferred habitats for microbes. Rhizodeposits are an important source of C and energy for microorganisms stimulating their growth and activity. Thereby, roots can influence the rate of native SOM decomposition in the rhizosphere. This rhizosphere priming effect (RPE) was reported to be plant-species specific. Therefore, we hypothesized that also plant inter-species interactions affect the RPE.&#13;
In Study 2, we used continuous 13CO2 labeling to investigate the RPE of monocultures and mixtures of typical agricultural crops. The RPE was consistently positive for all cultures with an increase of 43% - 136% above the unplanted soil. Of particular interest was the result that plant inter-species interactions between sunflower and wheat significantly reduced the RPE in contrast to mixtures which included soybean as a legume. It was argued that the RPE of the sunflower-wheat mixture was reduced through a more severe competition for nitrogen (N), whereas, due to the N-rich rhizodeposits of the legume and its lower demand for soil mineral N the RPE of the legume containing mixtures remained unaffected.&#13;
Besides potential plant-specific differences in the quality and quantity of rhizodeposits, also photosynthesis could control root exudation because of the fast transport of recently assimilated C to belowground pools. Taking both factors into account, in Studies 3 and 4 the effect of limited photosynthesis on the distribution of recently assimilated C, of stored C and of N was investigated. Based on 13C, 14C and 15N labeling of a legume and a non-legume we could demonstrate that high C and N demands of regrowing shoots after clipping led to a remobilization of stored C and N to the shoots. Additionally, recently assimilated C was retained in the regrowing shoots. &#13;
Shading, in contrast, did not induce a remobilization of stored C, since recently assimilated C obviously covered the demand of the shoots with lower growth rates. For both treatments lower amounts of recently assimilated C were observed in the belowground pools emphasizing the importance of the tight coupling of assimilation and belowground processes. Furthermore, different responses of clipping and shading of the legume and the non-legume could be detected for root-derived CO2. &#13;
The quantitative importance of rhizodeposition at field scale was determined in Study 5. We proposed a new approach for an improved quantification of rhizodeposition under field conditions taking into account the decomposed fraction of rhizodeposits. Based on a 14CO2 pulse labeling experiment under controlled conditions a rhizodeposition-to-root ratio was calculated and was applied to the root biomass of the field. The root biomass C of maize, sampled in July 2009, was 298±64 kg C ha-1. Gross rhizodeposition was 166±53 kg C ha-1. &#13;
With aging of SOM, the availability of C for microbial decomposition declines. In Study 6 the availability of younger relative to older C sources was assessed. The natural isotope abundances of 13C and 12C of SOM and CO2 were analyzed after a C3 to C4 vegetation change. The contribution of younger C, originating from the belowground C input by maize in the previous year, and that of older C sources, derived from the former C3 vegetation, to SOM and CO2 was determined. Comparing the proportions of younger and older C in SOM with that in CO2, we found that younger C was 7 times more available for microbial decomposition than older C pools.&#13;
In summary, this thesis extends the understanding of factors affecting rhizodeposition and of processes occurring at the soil-root interface. Furthermore, it presents a new method to quantify gross rhizodeposition at field scale. Although, we could gain insight in temporal changes of the availability of C pools for microbes, the ecological importance of C fluxes in the rhizosphere requires future research on this topic with regard to spatial and temporal predictions.&#13;
</description>
      <author>Johanna  Pausch</author>
      <category>doctoralthesis</category>
      <guid>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1066</guid>
      <pubDate>Wed, 06 Feb 2013 11:58:39 +0100</pubDate>
    </item>
    <item>
      <title>Comparisons of N2O and CH4 fluxes as affected by land use systems and climate in small catchments in Korea</title>
      <link>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1064</link>
      <description>In the course of global and climate change humankind has to face extreme weather events with increased intensity and frequency and it has to deal with feeding an increasing number of people which is accompanied by shortage of resources such as water. Since half of humankind directly depends on freshwater and other ecosystem services provided by mountainous areas, it is essential to study such complex terrains and how natural as well as agricultural systems react to climatic and other anthropogenic changes. &#13;
Emissions of greenhouse gases like Nitrous oxide (N2O) and Methane (CH4) are of global concern, too, because they are involved in global warming and therewith: climate change. Major sources of N2O are agriculturally managed soils, and very important sources of CH4 are rice paddies. Thus, it is of great importance to study intensively managed agricultural systems and the effects of the management practices on greenhouse gas emissions. &#13;
The major focus of this thesis is to quantify dry crop fields’ and forests’ N2O emissions as well as rice paddies’ N2O and CH4 emissions and to identify climatic as well as management related factors and underlying processes which are driving the N2O fluxes in a complex terrain. &#13;
A prolonged early summer drought in 2010 led to significant N2O consumption in soil of three different forest sites. The following above-average monsoon rainfall period indeed turned the N2O consumption into emission but could not turn the N2O balance of a forest on sandy-loam substrate from negative into a positive one, which means that for the first time a negative N2O balance was observed for a forest soil during the growing season. The N2O emissions of those forest sites were clearly driven by soil moisture and temperature and there appeared to be an effect of the substrate on N2O emissions as well, as it is increasingly often observed that sandy-loam soils show significant N2O consumption.&#13;
Plastic mulching – a worldwide used method in agriculture to increase crop production by enhancing soil temperature, creating more stable soil moisture conditions and restricting arable weed growth – turned out to have a mitigating effect on N2O emissions. DNDC (Denitrification and Decomposition) modeling results matched best with the measurement results when the maximum daily soil temperature and half of the daily precipitation was assumed to occur as dominating climate conditions underneath the impervious polyethylene (PE) film, suggesting that N2O production underneath the plastic cover was driven by soil moisture and temperature. N2O emissions from a non-fertilized soy bean field, which has Nitrogen fixation as an additional Nitrogen source, were similar to the N2O emissions from a radish field after application of an intermediate amount of N fertilizer of 200 kg ha-1.&#13;
 &#13;
Comparing N2O and CH4 emissions from rice paddies under different water management practices showed that intermittent irrigation (II) (no continuous flooding, no water logging)  &#13;
had the least global warming potential (GWP) which was only 30% of the global warming potential (GWP) of a traditionally irrigated (TI) paddy (continuous flooding and water logging). Another practice of 2.5 months of continuous flooding, followed by midseason drainage and reflooding which created moist but non-water logged conditions (FDFM) lead to 66% of the traditionally irrigated paddies combined CH4 and N2O emissions. These results suggest that a trend towards less flooding has a great potential to mitigate greenhouse gas emissions from a sandy or sandy-loam substrate, respectively. Studying the three paddies’ subsoil conditions revealed that N2O production and consumption processes had mainly taken place between 25 and 50 cm soil depth judging by N2O concentrations  and δ15N-N2O values along the soil profiles of all the investigated paddies as well as gene abundances of denitrifying and nitrifying bacteria of the FDFM paddy.&#13;
Apart from these important findings on N2O flux dynamics of three different land use systems, it is noticeable that the N2O emissions of the study region are in general very low which is very pleasing and implies that the area deals with global change challenges and associated intensive agriculture in a way that comparatively only small amounts of N2O degas. But this raises the question after the “why?” considering that large amounts of fertilizer are applied on the fields. This thesis does not have a final answer to that question but it discusses whether the sandy substrate may play a major role for the N dynamics of the whole area. There is evidence that NO3- - as the substrate for denitrification - leaches easily due to the soil conditions. To finally figure out why the N2O emissions are that low a more detailed investigation on the fate of NO3- would be desirable.</description>
      <author>Sina Berger</author>
      <category>doctoralthesis</category>
      <guid>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1064</guid>
      <pubDate>Mon, 04 Feb 2013 09:27:53 +0100</pubDate>
    </item>
    <item>
      <title>Intuitive Human-Robot Interaction by Intention Recognition</title>
      <link>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1079</link>
      <description>For two humans to interact with each other to perform a common task, they need to know the expectation of each other during interaction. For example if we consider an example of a waiter and a guest. If the waiter tilts the bottle to offer a drink to the guest then he may expect two actions from the guest, i.e., either the guest will forward his glass to get it filled or he will take his glass backward for not accepting the drink. If the guest forwards his glass then the waiter expects that the guest will keep his glass at a certain point until he pours the liquid into the glass. Similarly if the guest takes its glass backward then he expects from the waiter not to pour the liquid into his glass. In any case of misunderstanding an accident can occur. It applies to almost all the instances of human-human interaction. The recognition of the intention plays a key role in human-human interaction. It is equally important in human-robot interaction.&#13;
With the increase of research in the field of robotics, the robots are and will be becoming more and more part of human life. For the robots to be the effective part of the human life they should be helpful to the human. For a robot to be helpful to the human he should act according to the human. In case if the robot tries to help the human without knowing the intention of the interacting human then the robot can be itself a problem rather than a solution to the problems. Therefore it is necessary for a robot to know the intention of the human with whom the robot is supposed to interact to facilitate him.&#13;
The aim of this work is to propose a solution to make the human robot interaction intuitive. For making the human-robot interaction intuitive the intention of the human should be known to the interacting robot. A probabilistic approach is introduced to recognize the human intention. The approach uses the finite state machines. Each finite state machine representing a unique human intention carries a probabilistic value that is called the weight of the finite state machine. That weight tells the robot about the current human intention.&#13;
Since it is not possible to embed all the possible intentions into the robot that the robot may need to recognize. Thus, there should be a measure that the robot can learn new human intentions. An approach is discussed for this purpose.&#13;
For the human-robot interaction to be intelligent the robot should be quick in his response towards the human intention. An approach is described that addresses the issue of quick (proactive) response of the robot. The proposed approach also discusses the scenario concerning the ambiguous human intention. An ambiguous intention is a human intention that apparently corresponds to more than one human intention.&#13;
There may be a scenario in which the human has a totally new intention that the robot does not know already and also has not learned that intention. In this case, apparently there is no human- robot interaction. In order to cope with this problem an approach is discussed that enables the robot to select an appropriate action to interact with the human.&#13;
An approach concerning the generalization of the human intention is also discussed. By generalizing the human intention, the robot can extend its response according to the human intention. The extension of the response means that the robot takes those actions that were not instructed to him to be taken concerning the human intention.&#13;
</description>
      <author>Muhammad  Awais</author>
      <category>doctoralthesis</category>
      <guid>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1079</guid>
      <pubDate>Mon, 04 Feb 2013 09:16:53 +0100</pubDate>
    </item>
    <item>
      <title>Charge and excitation-energy transfer in time-dependent density functional theory</title>
      <link>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1075</link>
      <description>Learning about and understanding the mechanisms and pathways of charge and excitation-energy transfer of natural molecular complexes is a promising approach for the tailored design of new artificial energy-converting materials. Therefore, next to exten­sive experimental investigations, a theoretical method that is able to reliably describe and predict these phenomena from first principles is of practical relevance. In principle, density functional theory (DFT) and time-dependent density functional theory (TDDFT) appear as natural choices to study the relevant sizable molecules on a first-principles scale at bearable computational cost. However, the application of standard local and semilocal density functional approximations suffers from well-known deficiencies, in particular, as far as the simulation of charge-transfer pheno­mena is concerned. The present thesis approaches charge and excitation-energy trans­fer with the objective of improving the predictive power and extending the range of applicability of (TD)DFT. &#13;
&#13;
The deficiencies of standard density functional approximations have been related to self-interaction. Hence, one major aspect of this work is the extension of the self-inter­ac­tion correction in Kohn-Sham DFT that is based on the generalized optimized effec­tive potential to TDDFT using a real-time propagation approach. The multi­plicative Kohn-Sham potential allows for a transparent analysis of the exchange-corre­la­tion poten­tial during time evolution. It reveals frequency-dependent field-counter­acting be­ha­vior and step structures that appear in dynamic charge-transfer situations. The latter are important for the proper description of charge transfer. Self-interaction correc­tion allows to access many cases that are difficult for standard TDDFT ranging from chain-like systems over excitonic excitations in semiconductor nano­clusters to short- and long-range charge-transfer excitations. At the same time, it does not spoil the reasonable accuracy that already (semi)local functionals exhibit for local excita­tions. Moreover, the TDDFT perspective on self-interaction correction sheds new light also on the ground-state formalism. Complex degrees of freedom in the energy-mini­mi­zing transformation of the generalized optimized effective potential approach yield smoother orbital densities that appear more reasonable when inserted into approximate functionals in the self-interaction correction formalism. This work provides new insight into the use of different functional approximations. Last but not least, the influence of spin-symmetry breaking and step structures of the potential on the preference to transfer integer units of the elementary electric charge between largely separated donor and acceptor moieties is illustrated when static external electric fields are applied. This work has been reported in three publications and one submitted manuscript.&#13;
&#13;
In the field of excitation-energy transfer, recent discoveries of quantum coherence effects shed new light on the mechanisms behind energy-transfer rates. The latter are affected by a number of different properties of the isolated molecules, but involve also effects due to the environment of the system. This thesis addresses excitation-energy transfer phenomena from two perspectives. First, I use real-time propagation TDDFT to investigate the intermolecular coupling strength and the coupling mechanism between single fragments of supermolecular setups. These investigations base on standard closed quantum system TDDFT and exploit the coherent oscillation of excitation energy between separated molecules after the initial excitation process. Second, I use open quantum system ideas in the framework of TDDFT to study the influence of the system’s environment on the energy-transfer time scales and pathways in a circular arrangement of molecules using an effective energy-dissipation mechanism. The first part of these results is published. The second part is presented in this thesis and includes work in progress.</description>
      <author>Dirk Hofmann-Mees</author>
      <category>doctoralthesis</category>
      <guid>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1075</guid>
      <pubDate>Mon, 04 Feb 2013 09:06:18 +0100</pubDate>
    </item>
    <item>
      <title>Polyelectrolyte Coatings with Internal Hierarchy</title>
      <link>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1068</link>
      <description>The results presented in this thesis are focused on the surface modification by polyelectrolytes and polyelectrolyte copolymers. The internal structural hierarchy originate thereby from the self-assembly processes at different length scales. To generate different levels of hierarchy, the coatings were constructed by using either the layer-by-layer (LbL) deposition method (lateral chemical structure), the adsorption of supramolecular aggregates (lateral topographycal structure), or the combination of both. Using these techniques, one can control the properties of the coatings by varying the chemical structure of the polyelectrolytes, for instance, their charge density, thus providing a convenient way for their functionalization and the ability to tune properties of the surface. Therefore, we were working with systems which have variable charge densities. With this approach, we were able to produce thin and ultrathin nanostructured films with tunable properties and functionality.</description>
      <author>Julia Gensel</author>
      <category>doctoralthesis</category>
      <guid>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1068</guid>
      <pubDate>Tue, 29 Jan 2013 10:08:36 +0100</pubDate>
    </item>
    <item>
      <title>Synthesis and Combinatorial Optimization of Novel Star-Shaped Resist Materials for Lithographic Applications</title>
      <link>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1059</link>
      <description>Gordon Earle Moore predicted in the mid-1960s the cost-efficient doubling of transistors’ number on integrated circuits every two years – known as Moore’s Law. Leading companies orientates by the development of integrated circuits on this Moore’s Law and contributed to this prediction to come true up to the present. In so doing, the semiconductor industry drafts every two years aims to fulfill this prediction summarized in the so-called International Technology Roadmap for Semiconductors (ITRS). The ITRS lists guidelines for cost-effective progresses in performance of integrated circuits, e.g. design of integrated circuits, advancements of exposure tools and exposure techniques, and closely correlated resist materials. This thesis deals with the development of new resist materials and their combinatorial investigation concerning the performance in lithographic patterning. &#13;
The lithographic patterning procedure is a sequence of multiple processing steps and thus this procedure involves many processing variables interacting strongly with each other. For understanding and comprehensive investigation of such multi-variable dependent systems the development and implementation of combinatorial approaches were in the focus of this thesis. Furthermore this thesis is focused on the synthesis of new tailored resist materials for lithographic patterning. Star topology was the selected polymer architecture of this new resist material realized via the core-first atom transfer radical polymerization (ATRP) technique. The lithographic performance of electron beam lithography patterning was investigated for the resulting randomly distributed star terpolymers and star block copolymers by combinatorial libraries in view of features’ quality.&#13;
The first chapter deals with developed, adapted, and improved combinatorial techniques for thin film investigations in general and utilized for lithographic patterning investigations in particular. The lithographic patterning procedure of chemically amplified resist systems consists of various steps: film preparation, post apply bake (PAB) to remove residual solvent, exposure, post exposure bake (PEB) to activate the catalytic reaction, and development. For this rather complex process variable gradients were developed and adapted for each processing step to investigate and optimize the performance of especially new resist systems. For the film preparation a method was developed to prepare an internal material composition gradient. This was realized by a gradient extrudate prepared using two individual controllable syringe pumps and subsequent doctor-blading. The material composition gradient was verified by high performance liquid chromatography. The second (PAB) and also the fourth (PEB) processing step are both annealing processes of the resist film although they serve different purposes. For the investigation of such annealing processes temperature gradients were prepared adjustable in temperature range and temperature slope. This adjustability is ensured by the active heating and the active cooling source and also by the gap and the type of metal plate. For the third step exposure methods were developed to realize defined exposure dose gradients in very small areas of the resist film. Different exposure dose gradients were designed for photolithography as well as for electron beam lithography. For the latter case this dose gradient was programmed in the pattern design using the software which controls the electron beam during the exposure process. The dose gradient for photolithography investigations was realized by a special designed shadow mask. For the last processing step development a preliminary screening of the dissolubility conditions of the resist film was established utilizing quartz crystal microbalances. Based on this measured dissolubility behavior the time frame was set for development time gradients performed by a stepwise or continuously immersion of the resist films. Lastly two to three variable gradients were combined to binary or ternary combinatorial libraries, respectively. The ternary combinatorial libraries allow the investigation of three variables of the lithographic patterning process in one experiment. Thus it is possible to optimize a resist material system fast and efficiently in respect to resist performance.&#13;
In the second chapter a star-shaped teroligomer is reported as new high potential resist type for lithographic patterning purposes. The polymerization was carried out via the core-first ATRP route using a functionalized saccharose with eight initiating sites as core. Four star-shaped teroligomers were synthesized with varying target arm lengths. In addition a saccharose molecule was synthesized with an average number of 3.5 initiating sites and thus a star oligomer was realized with a reduced arm number but an identical core and similar arm length. As reference resist material a linear model oligomer was synthesized using ethyl 2-bromoisobutyrate as initiator. For all polymers narrow monomodal distributions were detected with polydispersity index values of lower than 1.1. Based on calibration polymerizations runs the monomer feed of the three used monomers was adapted to achieve targeted monomer incorporations for all teroligomers. The targeted monomer incorporation was copied from a currently industrially used linear teroligomer. One star oligomer was selected as proof of principle for the utilization of the star architecture for lithographic purposes. This new resist material was combinatorial investigated in a ternary library and thus optimized in one experiment concerning exposure dose, PEB temperature, and development time. The optimized patterns with a feature size of 100 nm and an excellent line edge roughness (LER) value of 3.1 nm were observed.&#13;
The last chapter of this thesis demonstrates the straight forward advancement of the star-shaped resist material reported in chapter two. The statistical monomer incorporation was exchanged by the introduction of the tailored star block copolymer architecture. This architecture was synthesized for the first time via the core-first ATRP route by full conversion of a first polar monomer and in-situ polymerization of additionally added nonpolar monomer. The successful syntheses were indicated by contact angle measurements showing increased hydrophobicity of star block copolymers in contrast to random star copolymers with the same monomer incorporation. The star block copolymers exhibited also enhanced dissolubility behavior characterized by quartz crystal microbalance measurements. Furthermore they demonstrated an up to eight times increased sensitivity at their lithographic application in contrast to the synthesized reference linear copolymer. The most promising star block copolymer was selected to investigate its lithographic performance. The optimization was performed in a ternary combinatorial library based on the gradient variables exposure dose and feature size, PEB temperature, and development time. The optimized pattern of clear lines and a feature size of 66 nm was observed with a LER value of 6 nm.&#13;
To conclude, different tailored star-shaped terpolymers were synthesized using the ATRP core-first route and successfully applied in the lithographic patterning process for the first time. In addition the combinatorial optimization offers the absolutely promising potential of utilizing these star shaped resist materials by the demonstrated brilliant LER values, the achieved extremely high sensitivity, and the fast and efficient development of clear 66 nm lines.&#13;
</description>
      <author>Florian Wieberger</author>
      <category>doctoralthesis</category>
      <guid>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1059</guid>
      <pubDate>Thu, 17 Jan 2013 10:15:33 +0100</pubDate>
    </item>
    <item>
      <title>Mesostrukturierte Metalloxide und Polyoxometallate mittels Ionogener Diblockcopolymere - Synthese, Charakterisierung und Anwendung</title>
      <link>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1054</link>
      <description>Das Ziel der vorliegenden Arbeit war es, Metalloxide und Polyoxometallate auf der Mesoebene mittels ionogener Diblockcopolymere zu strukturieren, zu charakterisieren und anwendungsspezifisch zu testen. Dabei wurden vor allem drei bisher bekannte Probleme, die mit der Mesostrukturierung von Metalloxiden einhergehen, umgangen. &#13;
Zum einen führt die schnelle Hydrolyse und Kondensation reaktiver Metallalkoxid-Precursoren zu unstrukturierbar großen Molekülen. Zum anderen ist oftmals ein direkter Zugang zu der gewünschten Morphologie aufgrund der mizellaren Dynamik des Templates, die von äußeren Einflüssen, wie pH-Wert, Konzentration oder Salzkonzentration abhängt, erschwert. Das dritte Problem ist die schlechte Anbindung des anorganischen Precursors an das organische Templat, was auf schwache, attraktive Wechselwirkungen zwischen beiden Materialien zurückzuführen ist. Generell müssen Hydrolyse, Kondensation und Hybridbildung zwingend synchron ablaufen, um eine Makrophasenseparation zuverlässig zu vermeiden.&#13;
Um diese Makrophasenseparation zu vermeiden, wurde am Lehrstuhl AC I ein neuartiges Konzept entwickelt, in dem alle drei Probleme adressiert und gelöst werden konnten. Diese Lösungsansätze werden nachfolgend entsprechend ihrer oben aufgeführten Reihenfolge erklärt. Zunächst wurden anionische oligomere Cluster oder pre-synthetisierte Kolloide als anorganische Precursoren verwendet, anstelle schnell hydrolyisierender und kondensierender Metallalkoxide. Die Cluster besetzen energetische Minima auf dem Weg zu ausgedehnten Oxidstrukturen und neigen somit nicht zur Kondensation. Weiterhin konnte mit 1-dimensionalen kernquervernetzten Polymerbürsten die mizellare Dynamik umgangen werden, da die rigiden zylindrischen Polymerbürsten invariant gegenüber äußeren Einflüssen sind. Außerdem besitzen diese 1-dimensionalen Nanoobjekte ionisierbare Seitenarme, welche einfach protoniert werden können und somit über starke Coulomb-Wechselwirkungen eine stabile Anbindung der anorganischen Oxide an das organische Templat gewährleisten.&#13;
Dieses Konzept der ladungsinduzierten Mesostrukturierung mittels molekularer oxidischer Precursoren wurde innerhalb dieser Doktorarbeit weitergeführt, deren Ergebnisse nachfolgend kurz dargestellt werden.&#13;
Zuerst wurde am Beispiel von pre-synthetisierten Rutil- und Anatas-Kolloiden gezeigt, dass nicht nur anionische oligomere Cluster, sondern auch Kolloide in 1-dimensionale Poylmerstrukturen eingelagert werden können. Die Kristallstruktur von Rutil und Anatas konnte durch Verwendung unterschiedlicher Säuren (HCl: Rutil; Essigsäure: Anatas) bei der Hydrolyse des Titanalkoxid-Precursors gezielt eingestellt werden. Diese TiO2-Polymorphe besitzen bei niedrigen pH-Werten eine positive Oberflächenladung. Polystyrolsulfonsäure-block-polyallylmethacrylat (PSS-b-PAMA) wurde in Zusammenarbeit mit dem Lehrstuhl MCII als zylindrischer anionischer Antagonist synthetisiert. Die PSS-Seitenarme sind selbst bei niedrigen pH-Werten noch negativ geladen. Die resultierenden 1-dimensionalen Hybridmaterialien besaßen dieselbe Kristallstruktur wie der Precursor, eine homogene Verteilung der Nanopartikel in der Polymermatrix und nach Trocknung eine verschlaufte, sphaghetti-ähnliche Mikrostruktur mit relativ hoher spezifischer Oberfläche. &#13;
In einer detaillierteren Studie wurde zusätzlich der Einfluss der Länge der zylindrischen Template auf die Packung der 1-dimensionalen Nanoobjekte und auf die daraus resultierende spezifische Oberfläche untersucht. Dabei wurden zylindrische Hybridmaterialien aus Heteropolysäuren des Keggin-Typ Polyoxometallates (Keggin POM), die in 1-dimensionale Polybutadien-block-poly(2-vinylpyridin) (PB-b-P2VP) Polymerbürsten eingelagert wurden, verwendet. Hierbei zeigte sich insbesondere, dass eine kurze Ultraschallbehandlungsdauer das Aspektverhältnis der 1-dimensionalen Strukturen nur gering verändert, die Dispersion der anisotropen Hybridmaterialien perfektioniert und die interpartikulären Kontaktpunkte innerhalb der Mikrostruktur minimiert. Als Ergebnis wurde hierfür die maximal zugängliche spezifische Oberfläche erhalten. Eine Ausweitung dieses Syntheseprotokolls auf Keggin POMs mit unterschiedlicher Ladung, Heteroatomen und Metallkationen konnte auch erfolgreich durchgeführt werden. Katalysetests dieser Hybridzylinder offenbarten dabei Unterschiede in der Aktivität dieser Nanostäbchen in der sauer katalysierten Zersetzung von Isopropanol. &#13;
Angliedernd an die ladungsinduzierten Mesostrukturierung wurde ein neues Synthesekonzept zu invers hexagonal geordneten Polymer/ Keggin POM Mesostrukturen erarbeitet. Als organisches Templat wurde Polybutadien-block-poly(2-dimethylaminoethylmethacrylat) (PB-b-PDMAEMA) mit einem hohen Polymerisations-grad des PB-Blockes synthetisiert. Als weitere Schlüsselfaktoren erwiesen sich neben diesem hohen Polymerisationsgrad des PB-Blockes die Wahl des Lösungsmittel und der Keggin POM-Anteil. Um dieses Material auch für Anwendungen wie der Katalyse ansprechend zu machen, muss das polymere Templat am besten vollständig entfernt werden, um eine möglichst hohe Zugänglichkeit der aktiven Zentren zu gewährleisten. Dies wurde sowohl thermisch als auch mit aggressiveren Methoden versucht. Zum einen wurde durch systematische Studien zur thermischen Entfernung des Templates gezeigt, dass die Mesostruktur kollabiert bevor der Kohlenstoff komplett entfernt werden kann. Zum anderen wurde durch aggressivere Methoden, wie Plasmaätzen, erfolgreich der Zugang zu den Mesoporen an Ultradünnschnitten (&lt;50 nm) realisiert. An die thermische Behandlung reihte sich auch die Umwandlung der geordneten Mesophasen in geordnete Carbid/ Kohlenstoff-Nanokomposite an. Letztere sind für Katalyse oder Ladungsspeicherung auch wissenschaftlich interessant. Für die Umwandlung der geordneten oxidischen Mesophasen in Carbid/ Kohlenstoff Nanokomposite wurde nicht versucht das polymere Templat in den Poren zu entfernen, sondern es wurde zum ersten Mal als Kohlenstoffquelle in der Carbidisierungsreaktion verwendet. Folglich lieferten die hergestellten geordneten Mesophasen einen direkten und einfachen Zugang zu porösen Carbid/ Kohlenstoff Nanokompositen und zeigten katalytische Aktivität in der Zersetzung von Ammoniak.&#13;
Diese Arbeit ist eine kumulative Dissertation. Die detaillierten Ergebnisse werden in den angehängten Publikationen beschrieben.&#13;
</description>
      <author>Thomas Lunkenbein</author>
      <category>doctoralthesis</category>
      <guid>http://opus4.kobv.de/opus4-ubbayreuth/frontdoor/index/index/docId/1054</guid>
      <pubDate>Wed, 16 Jan 2013 08:49:41 +0100</pubDate>
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