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In this work, the development of temperature- and protein-responsive sensor materials based on biocompatible, inverse hydrogel opals (IHOs) is presented. With these materials, large biomolecules can be specifically recognised and the binding event visualised. The preparation of the IHOs was performed with a template process, for which monodisperse silica particles were vertically deposited onto glass slides as the first step. The obtained colloidal crystals with a thickness of 5 μm displayed opalescent reflections because of the uniform alignment of the colloids. As a second step, the template was embedded in a matrix consisting of biocompatible, thermoresponsive hydrogels. The comonomers were selected from the family of oligo(ethylene glycol)methacrylates. The monomer solution was injected into a polymerisation mould, which contained the colloidal crystals as a template. The space in-between the template particles was filled with the monomer solution and the hydrogel was cured via UV-polymerisation. The particles were chemically etched, which resulted in a porous inner structure. The uniform alignment of the pores and therefore the opalescent reflection were maintained, so these system were denoted as inverse hydrogel opals. A pore diameter of several hundred nanometres as well as interconnections between the pores should facilitate a diffusion of bigger (bio)molecules, which was always a challenge in the presented systems until now. The copolymer composition was chosen to result in a hydrogel collapse over 35 °C. All hydrogels showed pronounced swelling in water below the critical temperature. The incorporation of a reactive monomer with hydroxyl groups ensured a potential coupling group for the introduction of recognition units for analytes, e.g. proteins. As a test system, biotin as a recognition unit for avidin was coupled to the IHO via polymer-analogous Steglich esterification. The amount of accessible biotin was quantified with a colorimetric binding assay. When avidin was added to the biotinylated IHO, the wavelength of the opalescent reflection was significantly shifted and therefore the binding event was visualised. This effect is based on the change in swelling behaviour of the hydrogel after binding of the hydrophilic avidin, which is amplified by the thermoresponsive nature of the hydrogel. A swelling or shrinking of the pores induces a change in distance of the crystal planes, which are responsible for the colour of the reflection. With these findings, the possibility of creating sensor materials or additional biomolecules in the size range of avidin is given.
The sharply rising level of atmospheric carbon dioxide resulting from anthropogenic emissions is one of the greatest environmental concerns facing our civilization today. Metal-organic frameworks (MOFs) are a new class of materials that constructed by metal-containing nodes bonded to organic bridging ligands. MOFs could serve as an ideal platform for the development of next generation CO2 capture materials owing to their large capacity for the adsorption of gases and their structural and chemical tunability. The ability to rationally select the framework components is expected to allow the affinity of the internal pore surface toward CO2 to be precisely controlled, facilitating materials properties that are optimized for the specific type of CO2 capture to be performed (post-combustion capture, precombustion capture, or oxy-fuel combustion) and potentially even for the specific power plant in which the capture system is to be installed. For this reason, significant effort has been made in recent years in improving the gas separation performance of MOFs and some studies evaluating the prospects of deploying these materials in real-world CO2 capture systems have begun to emerge. We have developed six new MOFs, denoted as IFPs (IFP-5, -6, -7, -8, -9, -10, IFP = Imidazolate Framework Potsdam) and two hydrogen-bonded molecular building block (MBB, named as 1 and 2 for Zn and Co based, respectively) have been synthesized, characterized and applied for gas storage. The structure of IFP possesses 1D hexagonal channels. Metal centre and the substituent groups of C2 position of the linker protrude into the open channels and determine their accessible diameter. Interestingly, the channel diameters (range : 0.3 to 5.2 Å) for IFP structures are tuned by the metal centre (Zn, Co and Cd) and substituent of C2 position of the imidazolate linker. Moreover hydrogen bonded MBB of 1 and 2 is formed an in situ functionalization of a ligand under solvothermal condition. Two different types of channels are observed for 1 and 2. Materials contain solvent accessible void space. Solvent could be easily removed by under high vacuum. The porous framework has maintained the crystalline integrity even without solvent molecules. N2, H2, CO2 and CH4 gas sorption isotherms were performed. Gas uptake capacities are comparable with other frameworks. Gas uptake capacity is reduced when the channel diameter is narrow. For example, the channel diameter of IFP-5 (channel diameter: 3.8 Å) is slightly lower than that of IFP-1 (channel diameter: 4.2 Å); hence, the gas uptake capacity and Brunauer-Emmett-Teller (BET) surface area are slightly lower than IFP-1. The selectivity does not depend only on the size of the gas components (kinetic diameter: CO2 3.3 Å, N2 3.6 Å and CH4 3.8 ) but also on the polarizability of the surface and of the gas components. IFP-5 and-6 have the potential applications for the separation of CO2 and CH4 from N2-containing gas mixtures and CO2 and CH4 containing gas mixtures. Gas sorption isotherms of IFP-7, -8, -9, -10 exhibited hysteretic behavior due to flexible alkoxy (e.g., methoxy and ethoxy) substituents. Such phenomenon is a kind of gate effects which is rarely observed in microporous MOFs. IFP-7 (Zn-centred) has a flexible methoxy substituent. This is the first example where a flexible methoxy substituent shows the gate opening behavior in a MOF. Presence of methoxy functional group at the hexagonal channels, IFP-7 acted as molecular gate for N2 gas. Due to polar methoxy group and channel walls, wide hysteretic isotherm was observed during gas uptake. The N2 The estimated BET surface area for 1 is 471 m2 g-1 and the Langmuir surface area is 570 m2 g-1. However, such surface area is slightly higher than azolate-based hydrogen-bonded supramolecular assemblies and also comparable and higher than some hydrogen-bonded porous organic molecules.
Within the course of this thesis, I have investigated the complex interplay between electron and lattice dynamics in nanostructures of perovskite oxides. Femtosecond hard X-ray pulses were utilized to probe the evolution of atomic rearrangement directly, which is driven by ultrafast optical excitation of electrons. The physics of complex materials with a large number of degrees of freedom can be interpreted once the exact fingerprint of ultrafast lattice dynamics in time-resolved X-ray diffraction experiments for a simple model system is well known. The motion of atoms in a crystal can be probed directly and in real-time by femtosecond pulses of hard X-ray radiation in a pump-probe scheme. In order to provide such ultrashort X-ray pulses, I have built up a laser-driven plasma X-ray source. The setup was extended by a stable goniometer, a two-dimensional X-ray detector and a cryogen-free cryostat. The data acquisition routines of the diffractometer for these ultrafast X-ray diffraction experiments were further improved in terms of signal-to-noise ratio and angular resolution. The implementation of a high-speed reciprocal-space mapping technique allowed for a two-dimensional structural analysis with femtosecond temporal resolution. I have studied the ultrafast lattice dynamics, namely the excitation and propagation of coherent phonons, in photoexcited thin films and superlattice structures of the metallic perovskite SrRuO3. Due to the quasi-instantaneous coupling of the lattice to the optically excited electrons in this material a spatially and temporally well-defined thermal stress profile is generated in SrRuO3. This enables understanding the effect of the resulting coherent lattice dynamics in time-resolved X-ray diffraction data in great detail, e.g. the appearance of a transient Bragg peak splitting in both thin films and superlattice structures of SrRuO3. In addition, a comprehensive simulation toolbox to calculate the ultrafast lattice dynamics and the resulting X-ray diffraction response in photoexcited one-dimensional crystalline structures was developed in this thesis work. With the powerful experimental and theoretical framework at hand, I have studied the excitation and propagation of coherent phonons in more complex material systems. In particular, I have revealed strongly localized charge carriers after above-bandgap femtosecond photoexcitation of the prototypical multiferroic BiFeO3, which are the origin of a quasi-instantaneous and spatially inhomogeneous stress that drives coherent phonons in a thin film of the multiferroic. In a structurally imperfect thin film of the ferroelectric Pb(Zr0.2Ti0.8)O3, the ultrafast reciprocal-space mapping technique was applied to follow a purely strain-induced change of mosaicity on a picosecond time scale. These results point to a strong coupling of in- and out-of-plane atomic motion exclusively mediated by structural defects.
Cloud computing is a model for enabling on-demand access to a shared pool of computing resources. With virtually limitless on-demand resources, a cloud environment enables the hosted Internet application to quickly cope when there is an increase in the workload. However, the overhead of provisioning resources exposes the Internet application to periods of under-provisioning and performance degradation. Moreover, the performance interference, due to the consolidation in the cloud environment, complicates the performance management of the Internet applications. In this dissertation, we propose two approaches to mitigate the impact of the resources provisioning overhead. The first approach employs control theory to scale resources vertically and cope fast with workload. This approach assumes that the provider has knowledge and control over the platform running in the virtual machines (VMs), which limits it to Platform as a Service (PaaS) and Software as a Service (SaaS) providers. The second approach is a customer-side one that deals with the horizontal scalability in an Infrastructure as a Service (IaaS) model. It addresses the trade-off problem between cost and performance with a multi-goal optimization solution. This approach finds the scale thresholds that achieve the highest performance with the lowest increase in the cost. Moreover, the second approach employs a proposed time series forecasting algorithm to scale the application proactively and avoid under-utilization periods. Furthermore, to mitigate the interference impact on the Internet application performance, we developed a system which finds and eliminates the VMs suffering from performance interference. The developed system is a light-weight solution which does not imply provider involvement. To evaluate our approaches and the designed algorithms at large-scale level, we developed a simulator called (ScaleSim). In the simulator, we implemented scalability components acting as the scalability components of Amazon EC2. The current scalability implementation in Amazon EC2 is used as a reference point for evaluating the improvement in the scalable application performance. ScaleSim is fed with realistic models of the RUBiS benchmark extracted from the real environment. The workload is generated from the access logs of the 1998 world cup website. The results show that optimizing the scalability thresholds and adopting proactive scalability can mitigate 88% of the resources provisioning overhead impact with only a 9% increase in the cost.
Lakes are increasingly being recognized as an important component of the global carbon cycle, yet anthropogenic activities that alter their community structure may change the way they transport and process carbon. This research focuses on the relationship between carbon cycling and community structure of primary producers in small, shallow lakes, which are the most abundant lake type in the world, and furthermore subject to intense terrestrial-aquatic coupling due to their high perimeter:area ratio. Shifts between macrophyte and phytoplankton dominance are widespread and common in shallow lakes, with potentially large consequences to regional carbon cycling. I thus compared a lake with clear-water conditions and a submerged macrophyte community to a turbid, phytoplankton-dominated lake, describing differences in the availability, processing, and export of organic and inorganic carbon. I furthermore examined the effects of increasing terrestrial carbon inputs on internal carbon cycling processes. Pelagic diel (24-hour) oxygen curves and independent fluorometric approaches of individual primary producers together indicated that the presence of a submerged macrophyte community facilitated higher annual rates of gross primary production than could be supported in a phytoplankton-dominated lake at similar nutrient concentrations. A simple model constructed from the empirical data suggested that this difference between regime types could be common in moderately eutrophic lakes with mean depths under three to four meters, where benthic primary production is a potentially major contributor to the whole-lake primary production. It thus appears likely that a regime shift from macrophyte to phytoplankton dominance in shallow lakes would typically decrease the quantity of autochthonous organic carbon available to lake food webs. Sediment core analyses indicated that a regime shift from macrophyte to phytoplankton dominance was associated with a four-fold increase in carbon burial rates, signalling a major change in lake carbon cycling dynamics. Carbon mass balances suggested that increasing carbon burial rates were not due to an increase in primary production or allochthonous loading, but instead were due to a higher carbon burial efficiency (carbon burial / carbon deposition). This, in turn, was associated with diminished benthic mineralization rates and an increase in calcite precipitation, together resulting in lower surface carbon dioxide emissions. Finally, a period of unusually high precipitation led to rising water levels, resulting in a feedback loop linking increasing concentrations of dissolved organic carbon (DOC) to severely anoxic conditions in the phytoplankton-dominated system. High water levels and DOC concentrations diminished benthic primary production (via shading) and boosted pelagic respiration rates, diminishing the hypolimnetic oxygen supply. The resulting anoxia created redox conditions which led to a major release of nutrients, DOC, and iron from the sediments. This further transformed the lake metabolism, providing a prolonged summertime anoxia below a water depth of 1 m, and leading to the near-complete loss of fish and macroinvertebrates. Pelagic pH levels also decreased significantly, increasing surface carbon dioxide emissions by an order of magnitude compared to previous years. Altogether, this thesis adds an important body of knowledge to our understanding of the significance of the benthic zone to carbon cycling in shallow lakes. The contribution of the benthic zone towards whole-lake primary production was quantified, and was identified as an important but vulnerable site for primary production. Benthic mineralization rates were furthermore found to influence carbon burial and surface emission rates, and benthic primary productivity played an important role in determining hypolimnetic oxygen availability, thus controlling the internal sediment loading of nutrients and carbon. This thesis also uniquely demonstrates that the ecological community structure (i.e. stable regime) of a eutrophic, shallow lake can significantly influence carbon availability and processing. By changing carbon cycling pathways, regime shifts in shallow lakes may significantly alter the role of these ecosystems with respect to the global carbon cycle.
This thesis proposes a privacy protection framework for the controlled distribution and use of personal private data. The framework is based on the idea that privacy policies can be set directly by the data owner and can be automatically enforced against the data user. Data privacy continues to be a very important topic, as our dependency on electronic communication maintains its current growth, and private data is shared between multiple devices, users and locations. The growing amount and the ubiquitous availability of personal private data increases the likelihood of data misuse. Early privacy protection techniques, such as anonymous email and payment systems have focused on data avoidance and anonymous use of services. They did not take into account that data sharing cannot be avoided when people participate in electronic communication scenarios that involve social interactions. This leads to a situation where data is shared widely and uncontrollably and in most cases the data owner has no control over further distribution and use of personal private data. Previous efforts to integrate privacy awareness into data processing workflows have focused on the extension of existing access control frameworks with privacy aware functions or have analysed specific individual problems such as the expressiveness of policy languages. So far, very few implementations of integrated privacy protection mechanisms exist and can be studied to prove their effectiveness for privacy protection. Second level issues that stem from practical application of the implemented mechanisms, such as usability, life-time data management and changes in trustworthiness have received very little attention so far, mainly because they require actual implementations to be studied. Most existing privacy protection schemes silently assume that it is the privilege of the data user to define the contract under which personal private data is released. Such an approach simplifies policy management and policy enforcement for the data user, but leaves the data owner with a binary decision to submit or withhold his or her personal data based on the provided policy. We wanted to empower the data owner to express his or her privacy preferences through privacy policies that follow the so-called Owner-Retained Access Control (ORAC) model. ORAC has been proposed by McCollum, et al. as an alternate access control mechanism that leaves the authority over access decisions by the originator of the data. The data owner is given control over the release policy for his or her personal data, and he or she can set permissions or restrictions according to individually perceived trust values. Such a policy needs to be expressed in a coherent way and must allow the deterministic policy evaluation by different entities. The privacy policy also needs to be communicated from the data owner to the data user, so that it can be enforced. Data and policy are stored together as a Protected Data Object that follows the Sticky Policy paradigm as defined by Mont, et al. and others. We developed a unique policy combination approach that takes usability aspects for the creation and maintenance of policies into consideration. Our privacy policy consists of three parts: A Default Policy provides basic privacy protection if no specific rules have been entered by the data owner. An Owner Policy part allows the customisation of the default policy by the data owner. And a so-called Safety Policy guarantees that the data owner cannot specify disadvantageous policies, which, for example, exclude him or her from further access to the private data. The combined evaluation of these three policy-parts yields the necessary access decision. The automatic enforcement of privacy policies in our protection framework is supported by a reference monitor implementation. We started our work with the development of a client-side protection mechanism that allows the enforcement of data-use restrictions after private data has been released to the data user. The client-side enforcement component for data-use policies is based on a modified Java Security Framework. Privacy policies are translated into corresponding Java permissions that can be automatically enforced by the Java Security Manager. When we later extended our work to implement server-side protection mechanisms, we found several drawbacks for the privacy enforcement through the Java Security Framework. We solved this problem by extending our reference monitor design to use Aspect-Oriented Programming (AOP) and the Java Reflection API to intercept data accesses in existing applications and provide a way to enforce data owner-defined privacy policies for business applications.
The correction of software failures tends to be very cost-intensive because their debugging is an often time-consuming development activity. During this activity, developers largely attempt to understand what causes failures: Starting with a test case that reproduces the observable failure they have to follow failure causes on the infection chain back to the root cause (defect). This idealized procedure requires deep knowledge of the system and its behavior because failures and defects can be far apart from each other. Unfortunately, common debugging tools are inadequate for systematically investigating such infection chains in detail. Thus, developers have to rely primarily on their intuition and the localization of failure causes is not time-efficient. To prevent debugging by disorganized trial and error, experienced developers apply the scientific method and its systematic hypothesis-testing. However, even when using the scientific method, the search for failure causes can still be a laborious task. First, lacking expertise about the system makes it hard to understand incorrect behavior and to create reasonable hypotheses. Second, contemporary debugging approaches provide no or only partial support for the scientific method. In this dissertation, we present test-driven fault navigation as a debugging guide for localizing reproducible failures with the scientific method. Based on the analysis of passing and failing test cases, we reveal anomalies and integrate them into a breadth-first search that leads developers to defects. This systematic search consists of four specific navigation techniques that together support the creation, evaluation, and refinement of failure cause hypotheses for the scientific method. First, structure navigation localizes suspicious system parts and restricts the initial search space. Second, team navigation recommends experienced developers for helping with failures. Third, behavior navigation allows developers to follow emphasized infection chains back to root causes. Fourth, state navigation identifies corrupted state and reveals parts of the infection chain automatically. We implement test-driven fault navigation in our Path Tools framework for the Squeak/Smalltalk development environment and limit its computation cost with the help of our incremental dynamic analysis. This lightweight dynamic analysis ensures an immediate debugging experience with our tools by splitting the run-time overhead over multiple test runs depending on developers’ needs. Hence, our test-driven fault navigation in combination with our incremental dynamic analysis answers important questions in a short time: where to start debugging, who understands failure causes best, what happened before failures, and which state properties are infected.
Background: Increased numbers of intestinal E. coli are observed in inflammatory bowel disease, but the reasons for this proliferation and it exact role in intestinal inflammation are unknown. Aim of this PhD-project was to identify E. coli proteins involved in E. coli’s adaptation to the inflammatory conditions in the gut and to investigate whether these factors affect the host. Furthermore, the molecular basis for strain-specific differences between probiotic and harmful E. coli in their response to intestinal inflammation was investigated. Methods: Using mice monoassociated either with the adherent-invasive E. coli (AIEC) strain UNC or the probiotic E. coli Nissle, two different mouse models of intestinal inflammation were analysed: On the one hand, severe inflammation was induced by treating mice with 3.5% dextran sodium sulphate (DSS). On the other hand, a very mild intestinal inflammation was generated by associating interleukin 10-deficient (IL-10-/-) mice with E. coli. Differentially expressed proteins in the E. coli strains collected from caecal contents of these mice were identified by two-dimensional fluorescence difference gel electrophoresis. Results DSS-experiment: All DSS-treated mice revealed signs of a moderate caecal and a severe colonic inflammation. However, mice monoassociated with E. coli Nissle were less affected. In both E. coli strains, acute inflammation led to a downregulation of pathways involved in carbohydrate breakdown and energy generation. Accordingly, DSS-treated mice had lower caecal concentrations of bacterial fermentation products than the control mice. Differentially expressed proteins also included the Fe-S cluster repair protein NfuA, the tryptophanase TnaA, and the uncharacterised protein YggE. NfuA was upregulated nearly 3-fold in both E. coli strains after DSS administration. Reactive oxygen species produced during intestinal inflammation damage Fe-S clusters and thereby lead to an inactivation of Fe-S proteins. In vitro data indicated that the repair of Fe-S proteins by NfuA is a central mechanism in E. coli to survive oxidative stress. Expression of YggE, which has been reported to reduce the intracellular level of reactive oxygen species, was 4- to 8-fold higher in E. coli Nissle than in E. coli UNC under control and inflammatory conditions. In vitro growth experiments confirmed these results, indicating that E. coli Nissle is better equipped to cope with oxidative stress than E. coli UNC. Additionally, E. coli Nissle isolated from DSS-treated and control mice had TnaA levels 4- to 7-fold higher than E. coli UNC. In turn, caecal indole concentrations resulting from cleavage of tryptophan by TnaA were higher in E. coli Nissle- associated control mice than in the respective mice associated with E. coli UNC. Because of its anti-inflammatory effect, indole is hypothesised to be involved in the extension of the remission phase in ulcerative colitis described for E. coli Nissle. Results IL-10-/--experiment: Only IL-10-/- mice monoassociated with E. coli UNC for 8 weeks exhibited signs of a very mild caecal inflammation. In agreement with this weak inflammation, the variations in the bacterial proteome were small. Similar to the DSS-experiment, proteins downregulated by inflammation belong mainly to the central energy metabolism. In contrast to the DSS-experiment, no upregulation of chaperone proteins and NfuA were observed, indicating that these are strategies to overcome adverse effects of strong intestinal inflammation. The inhibitor of vertebrate C-type lysozyme, Ivy, was 2- to 3-fold upregulated on mRNA and protein level in E. coli Nissle in comparison to E. coli UNC isolated from IL-10-/- mice. By overexpressing ivy, it was demonstrated in vitro that Ivy contributes to a higher lysozyme resistance observed for E. coli Nissle, supporting the role of Ivy as a potential fitness factor in this E. coli strain. Conclusions: The results of this PhD-study demonstrate that intestinal bacteria sense even minimal changes in the health status of the host. While some bacterial adaptations to the inflammatory conditions are equal in response to strong and mild intestinal inflammation, other reactions are unique to a specific disease state. In addition, probiotic and colitogenic E. coli differ in their response to the intestinal inflammation and thereby may influence the host in different ways.
Agriculture is one of the most important human activities providing food and more agricultural goods for seven billion people around the world and is of special importance in sub-Saharan Africa. The majority of people depends on the agricultural sector for their livelihoods and will suffer from negative climate change impacts on agriculture until the middle and end of the 21st century, even more if weak governments, economic crises or violent conflicts endanger the countries’ food security. The impact of temperature increases and changing precipitation patterns on agricultural vegetation motivated this thesis in the first place. Analyzing the potentials of reducing negative climate change impacts by adapting crop management to changing climate is a second objective of the thesis. As a precondition for simulating climate change impacts on agricultural crops with a global crop model first the timing of sowing in the tropics was improved and validated as this is an important factor determining the length and timing of the crops´ development phases, the occurrence of water stress and final crop yield. Crop yields are projected to decline in most regions which is evident from the results of this thesis, but the uncertainties that exist in climate projections and in the efficiency of adaptation options because of political, economical or institutional obstacles have to be considered. The effect of temperature increases and changing precipitation patterns on crop yields can be analyzed separately and varies in space across the continent. Southern Africa is clearly the region most susceptible to climate change, especially to precipitation changes. The Sahel north of 13° N and parts of Eastern Africa with short growing seasons below 120 days and limited wet season precipitation of less than 500 mm are also vulnerable to precipitation changes while in most other part of East and Central Africa, in contrast, the effect of temperature increase on crops overbalances the precipitation effect and is most pronounced in a band stretching from Angola to Ethiopia in the 2060s. The results of this thesis confirm the findings from previous studies on the magnitude of climate change impact on crops in sub-Saharan Africa but beyond that helps to understand the drivers of these changes and the potential of certain management strategies for adaptation in more detail. Crop yield changes depend on the initial growing conditions, on the magnitude of climate change, and on the crop, cropping system and adaptive capacity of African farmers which is only now evident from this comprehensive study for sub-Saharan Africa. Furthermore this study improves the representation of tropical cropping systems in a global crop model and considers the major food crops cultivated in sub-Saharan Africa and climate change impacts throughout the continent.
Cellulose is the most abundant biopolymer on earth. In this work it has been used, in various forms ranging from wood to fully processed laboratory grade microcrystalline cellulose, to synthesise a variety of metal and metal carbide nanoparticles and to establish structuring and patterning methodologies that produce highly functional nano-hybrids. To achieve this, the mechanisms governing the catalytic processes that bring about graphitised carbons in the presence of iron have been investigated. It was found that, when infusing cellulose with an aqueous iron salt solution and heating this mixture under inert atmosphere to 640 °C and above, a liquid eutectic mixture of iron and carbon with an atom ratio of approximately 1:1 forms. The eutectic droplets were monitored with in-situ TEM at the reaction temperature where they could be seen dissolving amorphous carbon and leaving behind a trail of graphitised carbon sheets and subsequently iron carbide nanoparticles. These transformations turned ordinary cellulose into a conductive and porous matrix that is well suited for catalytic applications. Despite these significant changes on the nanometre scale the shape of the matrix as a whole was retained with remarkable precision. This was exemplified by folding a sheet of cellulose paper into origami cranes and converting them via the temperature treatment in to magnetic facsimiles of those cranes. The study showed that the catalytic mechanisms derived from controlled systems and described in the literature can be transferred to synthetic concepts beyond the lab without loss of generality. Once the processes determining the transformation of cellulose into functional materials were understood, the concept could be extended to other metals and metal-combinations. Firstly, the procedure was utilised to produce different ternary iron carbides in the form of MxFeyC (M = W, Mn). None of those ternary carbides have thus far been produced in a nanoparticle form. The next part of this work encompassed combinations of iron with cobalt, nickel, palladium and copper. All of those metals were also probed alone in combination with cellulose. This produced elemental metal and metal alloy particles of low polydispersity and high stability. Both features are something that is typically not associated with high temperature syntheses and enables to connect the good size control with a scalable process. Each of the probed reactions resulted in phase pure, single crystalline, stable materials. After showing that cellulose is a good stabilising and separating agent for all the investigated types of nanoparticles, the focus of the work at hand is shifted towards probing the limits of the structuring and pattering capabilities of cellulose. Moreover possible post-processing techniques to further broaden the applicability of the materials are evaluated. This showed that, by choosing an appropriate paper, products ranging from stiff, self-sustaining monoliths to ultra-thin and very flexible cloths can be obtained after high temperature treatment. Furthermore cellulose has been demonstrated to be a very good substrate for many structuring and patterning techniques from origami folding to ink-jet printing. The thereby resulting products have been employed as electrodes, which was exemplified by electrodepositing copper onto them. Via ink-jet printing they have additionally been patterned and the resulting electrodes have also been post functionalised by electro-deposition of copper onto the graphitised (printed) parts of the samples. Lastly in a preliminary test the possibility of printing several metals simultaneously and thereby producing finely tuneable gradients from one metal to another have successfully been made. Starting from these concepts future experiments were outlined. The last chapter of this thesis concerned itself with alternative synthesis methods of the iron-carbon composite, thereby testing the robustness of the devolved reactions. By performing the synthesis with partly dissolved scrap metal and pieces of raw, dry wood, some progress for further use of the general synthesis technique were made. For example by using wood instead of processed cellulose all the established shaping techniques available for wooden objects, such as CNC milling or 3D prototyping, become accessible for the synthesis path. Also by using wood its intrinsic well defined porosity and the fact that large monoliths are obtained help expanding the prospect of using the composite. It was also demonstrated in this chapter that the resulting material can be applied for the environmentally important issue of waste water cleansing. Additionally to being made from renewable resources and by a cheap and easy one-pot synthesis, the material is recyclable, since the pollutants can be recovered by washing with ethanol. Most importantly this chapter covered experiments where the reaction was performed in a crude, home-built glass vessel, fuelled – with the help of a Fresnel lens – only by direct concentrated sunlight irradiation. This concept carries the thus far presented synthetic procedures from being common laboratory syntheses to a real world application. Based on cellulose, transition metals and simple equipment, this work enabled the easy one-pot synthesis of nano-ceramic and metal nanoparticle composites otherwise not readily accessible. Furthermore were structuring and patterning techniques and synthesis routes involving only renewable resources and environmentally benign procedures established here. Thereby it has laid the foundation for a multitude of applications and pointed towards several future projects reaching from fundamental research, to application focussed research and even and industry relevant engineering project was envisioned.
This study investigated the warm-temperate to tropical shallow-water Miocene carbonates of the Perfugas basin (Anglona area), northern Sardinia, Italy (Central Mediterranean). The aim of this study was to identify and document the existence and significance of early diagenesis in this carbonate system, especially the diagenetic history, which reflects the diagenetic potential in terms of skeletal mineralogy. The motivation behind the present study was to investigate the role that early cementation has over facies stabilization linked to differences in biotic associations in shallow-water settings. Principal to this was to unravel the amount, kind and distribution of early cements in this type of carbonates, in order to complement previous studies, and hence acquire a more global perspective on non-tropical carbonate settings. The shallow-buried Sedini Limestone Unit was investigated for variations on early diagenetic features, as well as for the type of biotic association, and oxygen and carbon stable isotope stratigraphy. Results showed, that particularly at the Perfugas basin (< 15 km2), which evolves in time from a ramp into a steep-flanked platform, shallow-water facies are characterized by a “transitional” type of biotic association. The biotic assemblages change gradually over time from a heterozoan-rich into a photozoan-rich depositional system. This transition implies a change in the depositional environmental control factors such as temperature. It is considered that sedimentation took place under warm-temperate waters, which shifted to more warmer or tropical waters through time. Moreover, it was noticed that along with these changes, marine early syn-depositional cements (high-Mg calcite), with particular fabrics (e.g. fibrous), gradually contributed to the early lithification of rocks, favoring a steepening of the platform relief. The major controls for the shift of the depositional geometry was triggered by the change of the type of biotic associations (carbonate factory), related with the shift towards warmer conditions, and the development of early marine cementation. The identification of the amount and distribution of different cement phases, porosities and early diagenetic features, within facies and stratigraphy, showed that diagenesis is differential along depth, and within the depositional setting. High-Mg calcite cements (micrite, fibrous and syntaxial inclusion-rich) are early syn-depositional, facies-related (shallow-water), predominant at the platform phase, and marine in origin. Low-Mg calcite cements (bladed, syntaxial inclusionpoor and blocky) are early to late post-depositional, non-facies related (shallow- to deep-water) and shallow-burial marine in origin. However, a particular difference exists when looking at the amount and distribution of low-Mg calcite bladed cements. They become richer in shallow-water facies at the platform phase, suggesting that the enrichment of bladed cementation is linked to the appearance of metastable grains (e.g. aragonite). In both depositional profiles, the development of secondary porosity is the product of fabric-selective dissolution of grains (aragonite, high-Mg calcite) and/or cements (syntaxial inclusion-rich). However, stratigraphy and stable isotopes (oxygen and carbon), indicate that the molds found at shallower facies located beneath, and close to stratigraphic boundaries, have been produced by the infiltration of meteoric-derived water, which caused recrystallization without calcite cementation. Away from these stratigraphic locations, shallow- and deep-water facies show molds, and recrystallization, as well as low-Mg calcite cementation, interpreted as occurring during burial of these sediments by marine waters. The main cement source is suggested to be aragonite. Our results indicate that the Sedini Limestone Unit was transformed in three different diagenetic environments (marine, meteoric and shallow-burial marine); however, the degree of transformation in each diagenetic environment differs in the heterozoan-dominated ramp from the photozoan-dominated platform. It is suggested that the sediments from the ramp follow a diagenetic pathway similar to their heterozoan counterparts (i.e. lack of marine cementation, and loss of primary porosity by compaction), and the sediments from the platform follow a diagenetic pathway similar to their photozoan counterparts (i.e. marine cementation occluding primary porosity). However, in this carbonate setting, cements are Mg-calcite, no meteoric cementation was produced, and secondary porosity at shallow-water facies of the platform phase is mostly open and preserved. Despite the temporal and transitional change in biotic associations, ramp and platform facies (shallow- to deep-water facies) showed an oxygen isotope record overprinted by diagenesis. Oxygen primary marine signatures were not found. It is believed that burial diagenesis (recrystallization and low-Mg calcite cementation) was the main reason. This was unexpected at the ramp, since heterozoan-rich carbonates can hold isotope values close to primary marine signals due to their low-Mg calcite original composition. Ramp and platform facies (shallow- to deep-water facies) showed a carbon isotope record that was less affected by diagenesis. However, only at deep-water facies, did the carbon record show positive values comparable with carbon primary marine signals. The positive carbon values were noticed with major frequency at the platform deep-water facies. Moreover, these values usually showed a covariant trend with the oxygen isotope record; even that the latter did not hold positive values. The main conclusion of this work is that carbonates, deposited under warm-temperate to tropical conditions, have a unique facies, diagenesis and chemostratigraphic expression, which is different from their cool-water heterozoan or warm-water photozoan counterparts, reflecting the “transitional” nature of biotic association.
Forests are a key resource serving a multitude of functions such as providing income to forest owners, supplying industries with timber, protecting water resources, and maintaining biodiversity. Recently much attention has been given to the role of forests in the global carbon cycle and their management for increased carbon sequestration as a possible mitigation option against climate change. Furthermore, the use of harvested wood can contribute to the reduction of atmospheric carbon through (i) carbon sequestration in wood products, (ii) the substitution of non-wood products with wood products, and (iii) through the use of wood as a biofuel to replace fossil fuels. Forest resource managers are challenged by the task to balance these multiple while simultaneously meeting economic requirements and taking into consideration the demands of stakeholder groups. Additionally, risks and uncertainties with regard to uncontrollable external variables such as climate have to be considered in the decision making process. In this study a scientific stakeholder dialogue with forest-related stakeholder groups in the Federal State of Brandenburg was accomplished. The main results of this dialogue were the definition of major forest functions (carbon sequestration, groundwater recharge, biodiversity, and timber production) and priority setting among them by the stakeholders using the pair-wise comparison technique. The impact of different forest management strategies and climate change scenarios on the main functions of forest ecosystems were evaluated at the Kleinsee management unit in south-east Brandenburg. Forest management strategies were simulated over 100 years using the forest growth model 4C and a wood product model (WPM). A current climate scenario and two climate change scenarios based on global circulation models (GCMs) HadCM2 and ECHAM4 were applied. The climate change scenario positively influenced stand productivity, carbon sequestration, and income. The impact on the other forest functions was small. Furthermore, the overall utility of forest management strategies were compared under the priority settings of stakeholders by a multi-criteria analysis (MCA) method. Significant differences in priority setting and the choice of an adequate management strategy were found for the environmentalists on one side and the more economy-oriented forest managers of public and private owned forests on the other side. From an ecological perspective, a conservation strategy would be preferable under all climate scenarios, but the business as usual management would also fit the expectations under the current climate. In contrast, a forest manager in public-owned forests or a private forest owner would prefer a management strategy with an intermediate thinning intensity and a high share of pine stands to enhance income from timber production while maintaining the other forest functions. The analysis served as an example for the combined application of simulation tools and a MCA method for the evaluation of management strategies under multi-purpose and multi-user settings with changing climatic conditions. Another focus was set on quantifying the overall effect of forest management on carbon sequestration in the forest sector and the wood industry sector plus substitution effects. To achieve this objective, the carbon emission reduction potential of material and energy substitution (Smat and Sen) was estimated based on a literature review. On average, for each tonne of dry wood used in a wood product substituting a non-wood product, 0.71 fewer tonnes of fossil carbon are emitted into to the atmosphere. Based on Smat and Sen, the calculation of the carbon emission reduction through substitution was implemented in the WPM. Carbon sequestration and substitution effects of management strategies were simulated at three local scales using the WPM and the forest growth models 4C (management unit level) or EFISCEN (federal state of Brandenburg and Germany). An investigation was conducted on the influence of uncertainties in the initialisation of the WPM, Smat, and basic conditions of the wood product sector on carbon sequestration. Results showed that carbon sequestration in the wood industry sector plus substitution effects exceeded sequestration in the forest sector. In contrast to the carbon pools in the forest sector, which acted as sink or source, the substitution effects continually reduced carbon emission as long as forests are managed and timber is harvested. The main climate protection function was investigated for energy substitution which accounted for about half of the total carbon sequestration, followed by carbon storage in landfills. In Germany, the absolute annual carbon sequestration in the forest and wood industry sector plus substitution effects was 19.9 Mt C. Over 50 years the wood industry sector contributed 70% of the total carbon sequestration plus substitution effects.
River reaches protected by dikes exhibit high damage potential due to strong value accumulation in the hinterland areas. While providing an efficient protection against low magnitude flood events, dikes may fail under the load of extreme water levels and long flood durations. Hazard and risk assessments for river reaches protected by dikes have not adequately considered the fluvial inundation processes up to now. Particularly, the processes of dike failures and their influence on the hinterland inundation and flood wave propagation lack comprehensive consideration. This study focuses on the development and application of a new modelling system which allows a comprehensive flood hazard assessment along diked river reaches under consideration of dike failures. The proposed Inundation Hazard Assessment Model (IHAM) represents a hybrid probabilistic-deterministic model. It comprises three models interactively coupled at runtime. These are: (1) 1D unsteady hydrodynamic model of river channel and floodplain flow between dikes, (2) probabilistic dike breach model which determines possible dike breach locations, breach widths and breach outflow discharges, and (3) 2D raster-based diffusion wave storage cell model of the hinterland areas behind the dikes. Due to the unsteady nature of the 1D and 2D coupled models, the dependence between hydraulic load at various locations along the reach is explicitly considered. The probabilistic dike breach model describes dike failures due to three failure mechanisms: overtopping, piping and slope instability caused by the seepage flow through the dike core (micro-instability). The 2D storage cell model driven by the breach outflow boundary conditions computes an extended spectrum of flood intensity indicators such as water depth, flow velocity, impulse, inundation duration and rate of water rise. IHAM is embedded in a Monte Carlo simulation in order to account for the natural variability of the flood generation processes reflected in the form of input hydrographs and for the randomness of dike failures given by breach locations, times and widths. The model was developed and tested on a ca. 91 km heavily diked river reach on the German part of the Elbe River between gauges Torgau and Vockerode. The reach is characterised by low slope and fairly flat extended hinterland areas. The scenario calculations for the developed synthetic input hydrographs for the main river and tributary were carried out for floods with return periods of T = 100, 200, 500, 1000 a. Based on the modelling results, probabilistic dike hazard maps could be generated that indicate the failure probability of each discretised dike section for every scenario magnitude. In the disaggregated display mode, the dike hazard maps indicate the failure probabilities for each considered breach mechanism. Besides the binary inundation patterns that indicate the probability of raster cells being inundated, IHAM generates probabilistic flood hazard maps. These maps display spatial patterns of the considered flood intensity indicators and their associated return periods. Finally, scenarios of polder deployment for the extreme floods with T = 200, 500, 1000 were simulated with IHAM. The developed IHAM simulation system represents a new scientific tool for studying fluvial inundation dynamics under extreme conditions incorporating effects of technical flood protection measures. With its major outputs in form of novel probabilistic inundation and dike hazard maps, the IHAM system has a high practical value for decision support in flood management.
This thesis aims to quantify the human impact on the natural resource water at the landscape scale. The drivers in the federal state of Brandenburg (Germany), the area under investigation, are land-use changes induced by policy decisions at European and federal state level. The water resources of the federal state are particularly sensitive to changes in land-use due to low precipitation rates in the summer combined with sandy soils and high evapotranspiration rates. Key elements in landscape hydrology are forests because of their unique capacity to transport water from the soil to the atmosphere. Given these circumstances, decisions made at any level of administration that may have effects on the forest sector in the state are critical in relation to the water cycle. It is therefore essential to evaluate any decision that may change forest area and structure in such a sensitive region. Thus, as a first step, it was necessary to develop and implement a model able to simulate possible interactions and feedbacks between forested surfaces and the hydrological cycle at the landscape scale. The result is a model for simulating the hydrological properties of forest stands based on a robust computation of the temporal and spatial LAI (leaf area index) dynamics. The approach allows the simulation of all relevant hydrological processes with a low parameter demand. It includes the interception of precipitation and transpiration of forest stands with and without groundwater in the rooting zone. The model also considers phenology, biomass allocation, as well as mortality and simple management practices. It has been implemented as a module in the eco-hydrological model SWIM (Soil and Water Integrated Model). This model has been tested in two pre-studies to verify the applicability of its hydrological process description for the hydrological conditions typical for the state. The newly implemented forest module has been tested for Scots Pine (Pinus sylvestris) and in parts for Common Oak (Quercus robur and Q. petraea) in Brandenburg. For Scots Pine the results demonstrate a good simulation of annual biomass increase and LAI in addition to the satisfactory simulation of litter production. A comparison of the simulated and measured data of the May sprout for Scots pine and leaf unfolding for Oak, as well as the evaluation against daily transpiration measurements for Scots Pine, does support the applicability of the approach. The interception of precipitation has also been simulated and compared with weekly observed data for a Scots Pine stand which displays satisfactory results in both the vegetation periods and annual sums. After the development and testing phase, the model is used to analyse the effects of two scenarios. The first scenario is an increase in forest area on abandoned agricultural land that is triggered by a decrease in European agricultural production support. The second one is a shift in species composition from predominant Scots Pine to Common Oak that is based on decisions of the regional forestry authority to support a more natural species composition. The scenario effects are modelled for the federal state of Brandenburg on a 50m grid utilising spatially explicit land-use patterns. The results, for the first scenario, suggest a negative impact of an increase in forest area (9.4% total state area) on the regional water balance, causing an increase in mean long-term annual evapotranspiration of 3.7% at 100% afforestation when compared to no afforestation. The relatively small annual change conceals a much more pronounced seasonal effect of a mean long-term evapotranspiration increase by 25.1% in the spring causing a pronounced reduction in groundwater recharge and runoff. The reduction causes a lag effect that aggravates the scarcity of water resources in the summer. In contrast, in the second scenario, a change in species composition in existing forests (29.2% total state area) from predominantly Scots Pine to Common Oak decreases the long-term annual mean evapotranspiration by 3.4%, accompanied by a much weaker, but apparent, seasonal pattern. Both scenarios exhibit a high spatial heterogeneity because of the distinct natural conditions in the different regions of the state. Areas with groundwater levels near the surface are particularly sensitive to changes in forest area and regions with relatively high proportion of forest respond strongly to the change in species composition. In both cases this regional response is masked by a smaller linear mean effect for the total state area. Two critical sources of uncertainty in the model results have been investigated. The first one originates from the model calibration parameters estimated in the pre-study for lowland regions, such as the federal state. The combined effect of the parameters, when changed within their physical meaningful limits, unveils an overestimation of the mean water balance by 1.6%. However, the distribution has a wide spread with 14.7% for the 90th percentile and -9.9% for the 10th percentile. The second source of uncertainty emerges from the parameterisation of the forest module. The analysis exhibits a standard deviation of 0.6 % over a ten year period in the mean of the simulated evapotranspiration as a result of variance in the key forest parameters. The analysis suggests that the combined uncertainty in the model results is dominated by the uncertainties of calibration parameters. Therefore, the effect of the first scenario might be underestimated because the calculated increase in evapotranspiration is too small. This may lead to an overestimation of the water balance towards runoff and groundwater recharge. The opposite can be assumed for the second scenario in which the decrease in evapotranspiration might be overestimated.
Adenylates are metabolites with essential function in metabolism and signaling in all living organisms. As Cofactors, they enable thermodynamically unfavorable reactions to be catalyzed enzymatically within cells. Outside the cell, adenylates are involved in signalling processes in animals and emerging evidence suggests similar signaling mechanisms in the plants’ apoplast. Presumably, apoplastic apyrases are involved in this signaling by hydrolyzing the signal mediating molecules ATP and ADP to AMP. This PhD thesis focused on the role of adenylates on metabolism and development of potato (Solanum tuberosum) by using reverse genetics and biochemical approaches. To study the short and long term effect of cellular ATP and the adenylate energy charge on potato tuber metabolism, an apyrase from Escherichia coli targeted into the amyloplast was expressed inducibly and constitutively. Both approaches led to the identification of adaptations to reduced ATP/energy charge levels on the molecular and developmental level. These comprised a reduction of metabolites and pathway fluxes that require significant amounts of ATP, like amino acid or starch synthesis, and an activation of processes that produce ATP, like respiration and an immense increase in the surface-to-volume ratio. To identify extracellular enzymes involved in adenylate conversion, green fluorescent protein and activity localization studies in potato tissue were carried out. It was found that extracellular ATP is imported into the cell by an apoplastic enzyme complement consisting of apyrase, unspecific phosphatase, adenosine nucleosidase and an adenine transport system. By changing the expression of a potato specific apyrase via transgenic approaches, it was found that this enzyme has strong impact on plant and particular tuber development in potato. Whereas metabolite levels were hardly altered, transcript profiling of tubers with reduced apyrase activity revealed a significant upregulation of genes coding for extensins, which are associated with polar growth. The results are discussed in context of adaptive responses of plants to changes in the adenylate levels and the proposed role of apyrase in apoplastic purinergic signaling and ATP salvaging. In summary, this thesis provides insight into adenylate regulated processes within and outside non-photosynthetic plant cells.
In semi-arid savannah ecosystems, the vegetation structure and composition, i.e. the architecture of trees, shrubs, grass tussocks and herbaceous plants, offer a great variety of habitats and niches to sustain animal diversity. In the last decades intensive human land use practises like livestock farming have altered the vegetation in savannah ecosystems worldwide. Extensive grazing leads to a reduction of the perennial and herbaceous vegetation cover, which results in an increased availability of bare soil. Both, the missing competition with perennial grasses and the increase of bare soils favour shrub on open ground and lead to area-wide shrub encroachment. As a consequence of the altered vegetation structure and composition, the structural diversity declines. It has been shown that with decreasing structural diversity animal diversity decline across a variety of taxa. Knowledge on the effects of overgrazing on reptiles, which are an important part of the ecosystem, are missing. Furthermore, the impact of habitat degradation on factors of a species population dynamic and life history, e.g., birth rate, survival rate, predation risk, space requirements or behavioural adaptations are poorly known. Therefore, I investigated the impact of overgrazing on the reptile community in the southern Kalahari. Secondly I analysed population dynamics and the behaviour of the Spotted Sand Lizard, Pedioplanis l. lineoocellata. All four chapters clearly demonstrate that habitat degradation caused by overgrazing had a severe negative impact upon (i) the reptile community as a whole and (ii) on population parameters of Pedioplanis l. lineoocellata. Chapter one showed a significant decline of regional reptile diversity and abundance in degraded habitats. In chapter two I demonstrated that P. lineoocellata moves more frequently, spends more time moving and covers larger distances in degraded than in non-degraded habitats. In addition, home range size of the lizard species increases in degraded habitats as shown by chapter three. Finally, chapter four showed the negative impacts of overgrazing on several population parameters of P. lineoocellata. Absolute population size of adult and juvenile lizards, survival rate and birth rate are significantly lower in degraded habitats. Furthermore, the predation risk was greatly increased in degraded habitats. A combination of a variety of aspects can explain the negative impact of habitat degradation on reptiles. First, reduced prey availability negatively affects survival rate, the birth rate and overall abundance. Second, the loss of perennial plant cover leads to a loss of niches and to a reduction of opportunities to thermoregulate. Furthermore, a loss of cover and is associated with increased predation risk. A major finding of my thesis is that the lizard P. lineoocellata can alter its foraging strategy. Species that are able to adapt and change behaviour, such as P. lineoocellata can effectively buffer against changes in their environment. Furthermore, perennial grass cover can be seen as a crucial ecological component of the vegetation in the semi-arid savannah system of the southern Kalahari. If perennial grass cover is reduced to a certain degree reptile diversity will decline and most other aspects of reptile life history will be negatively influenced. Savannah systems are characterised by a mixture of trees, shrubs and perennial grasses. These three vegetation components determine the composition and structure of the vegetation and accordingly influence the faunal diversity. Trees are viewed as keystone structures and focal points of animal activity for a variety of species. Trees supply animals with shelter, shade and food and act as safe sites, nesting sites, observation posts and foraging sites. Recent research demonstrates a positive influence of shrub patches on animal diversity. Moreover, it would seem that intermediate shrub cover can also sustain viable populations in savannah landscapes as has been demonstrated for small carnivores and rodent species. The influence of perennial grasses on faunal diversity did not receive the same attention as the influence of trees and shrubs. In my thesis I didn’t explicitly measure the direct effects of perennial grasses but my results strongly imply that it has an important role. If the perennial grass cover is significantly depleted my results suggest it will negatively influence reptile diversity and abundance and on several populations parameters of P. lineoocellata. Perennial grass cover is associated with the highest prey abundance, reptile diversity and reptile abundance. It provides reptiles both a refuge from predators and opportunities to optimise thermoregulation. The relevance of each of the three vegetation structural elements is different for each taxa and species. In conclusion, I can all three major vegetation structures in the savannah system are important for faunal diversity.
Phototropic microalgae have a large potential for producing valuable substances for the feed, food, cosmetics, pigment, bioremediation, and pharmacy industries as well as for biotechnological processes. Today it is estimated that the microalgal aquaculture worldwide production is 5000 tons of dry matter per year (not taking into account processed products) making it an approximately $1.25 billion U.S. per year industry. In this work, several spectroscopic techniques were utilized for the investigation of microalgae cells. Specifically, photondensity wave spectroscopy was applied as a technique for the on-line observation of the culture. For effective evaluation of the photosynthetic growth processes, fast and non-invasive sensor systems that analyze the relevant biological and technical process parameters are preferred. Traditionally, the biomass in a photobioreactor is quantified with the help of turbidimetry measurements, which require extensive calibration. Another problem frequently encountered when using spectral analysis for investigating solutions is that samples of interest are often undiluted and highly scattering and do not adhere to Beer-Lambert's law. Due to the fluorescence properties of chlorophyll, fluorescence spectroscopy techniques including fluorescence lifetime imaging and single photon counting could be applied to provide images of the cells as well as determine the effects of excitation intensity on the fluorescence lifetime, which is an indicator of the condition of the cell. A photon density wave is a sinusoidally intensity-modulated optical wave stemming from a point-source of light, which propagates through diffuse medium and exhibits amplitude and phase variations. Light propagation though strongly scattering media can be described by the P1 approximation to the Boltzmann transport equation. Photon density wave spectroscopy enables the ability to differentiate between scattered and absorbed light, which is desired so that an independent determination of the reduced scattering and absorption coefficients can be made. The absorption coefficient is related to the pigment content in the cells, and the reduced scattering coefficient can be used to characterize physical and morphological properties of the medium and was here applied for the determination of the average cell size.
I perform and analyse the first ever calculations of rotating stellar iron core collapse in {3+1} general relativity that start out with presupernova models from stellar evolutionary calculations and include a microphysical finite-temperature nuclear equation of state, an approximate scheme for electron capture during collapse and neutrino pressure effects. Based on the results of these calculations, I obtain the to-date most realistic estimates for the gravitational wave signal from collapse, bounce and the early postbounce phase of core collapse supernovae. I supplement my {3+1} GR hydrodynamic simulations with 2D Newtonian neutrino radiation-hydrodynamic supernova calculations focussing on (1) the late postbounce gravitational wave emission owing to convective overturn, anisotropic neutrino emission and protoneutron star pulsations, and (2) on the gravitational wave signature of accretion-induced collapse of white dwarfs to neutron stars.
Semiclassical asymptotics for the scattering amplitude in the presence of focal points at infinity
(2006)
We consider scattering in $\R^n$, $n\ge 2$, described by the Schr\"odinger operator $P(h)=-h^2\Delta+V$, where $V$ is a short-range potential. With the aid of Maslov theory, we give a geometrical formula for the semiclassical asymptotics as $h\to 0$ of the scattering amplitude $f(\omega_-,\omega_+;\lambda,h)$ $\omega_+\neq\omega_-$) which remains valid in the presence of focal points at infinity (caustics). Crucial for this analysis are precise estimates on the asymptotics of the classical phase trajectories and the relationship between caustics in euclidean phase space and caustics at infinity.
The layer-by-layer assembly (LBL) of polyelectrolytes has been extensively studied for the preparation of ultrathin films due to the versatility of the build-up process. The control of the permeability of these layers is particularly important as there are potential drug delivery applications. Multilayered polyelectrolyte microcapsules are also of great interest due to their possible use as microcontainers. This work will present two methods that can be used as employable drug delivery systems, both of which can encapsulate an active molecule and tune the release properties of the active species. Poly-(N-isopropyl acrylamide), (PNIPAM) is known to be a thermo-sensitive polymer that has a Lower Critical Solution Temperature (LCST) around 32oC; above this temperature PNIPAM is insoluble in water and collapses. It is also known that with the addition of salt, the LCST decreases. This work shows Differential Scanning Calorimetry (DSC) and Confocal Laser Scanning Microscopy (CLSM) evidence that the LCST of the PNIPAM can be tuned with salt type and concentration. Microcapsules were used to encapsulate this thermo-sensitive polymer, resulting in a reversible and tunable stimuli- responsive system. The encapsulation of the PNIPAM inside of the capsule was proven with Raman spectroscopy, DSC (bulk LCST measurements), AFM (thickness change), SEM (morphology change) and CLSM (in situ LCST measurement inside of the capsules). The exploitation of the capsules as a microcontainer is advantageous not only because of the protection the capsules give to the active molecules, but also because it facilitates easier transport. The second system investigated demonstrates the ability to reduce the permeability of polyelectrolyte multilayer films by the addition of charged wax particles. The incorporation of this hydrophobic coating leads to a reduced water sensitivity particularly after heating, which melts the wax, forming a barrier layer. This conclusion was proven with Neutron Reflectivity by showing the decreased presence of D2O in planar polyelectrolyte films after annealing creating a barrier layer. The permeability of capsules could also be decreased by the addition of a wax layer. This was proved by the increase in recovery time measured by Florescence Recovery After Photobleaching, (FRAP) measurements. In general two advanced methods, potentially suitable for drug delivery systems, have been proposed. In both cases, if biocompatible elements are used to fabricate the capsule wall, these systems provide a stable method of encapsulating active molecules. Stable encapsulation coupled with the ability to tune the wall thickness gives the ability to control the release profile of the molecule of interest.