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Nanostructured materials are materials consisting of nanoparticulate building blocks on the scale of nanometers (i.e. 10-9 m). Composition, crystallinity and morphology can enhance or even induce new properties of the materials, which are desirable for todays and future technological applications. In this work, we have shown new strategies to synthesise metal oxide and metal nitride nanomaterials. The first part of the work deals with the study of nonaqueous synthesis of metal oxide nanoparticles. We succeeded in the synthesis of In2O3 nanopartcles where we could clearly influence the morphology by varying the type of the precursors and the solvents; of ZnO mesocrystals by using acetonitrile as a solvent; of transition metal oxides (Nb2O5, Ta2O5 and HfO2) that are particularly hard to obtain on the nanoscale and other technologically important materials. Solvothermal synthesis however is not restricted to formation of oxide materials only. In the second part we show examples of nonaqueous, solvothermal reactions of metal nitrides, but the main focus lies on the investigation of the influence of different morphologies of metal oxide precursors on the formation of the metal nitride nanoparticles. In spite of various reports, the number and variety of nanocrystalline metal nitrides is marginally small by comparison to metal oxides; hence preformed metal oxides as precursors for the preparation of metal nitrides are a logical choice. By reacting oxide nanoparticles with cyanamide, urea or melamine, at temperatures of 800 to 900 °C under nitrogen flow metal nitrides could be obtained. We studied in detail the influence of the starting material and realized that size, crystallinity, type of nitrogen source and temperature play the most important role. We have managed to propose and verify a dissolution-recrystallisation model as the formation mechanism. Furthermore we could show that the initial morphology of the oxides could be retained when ammonia flow was used instead.
This PhD thesis presents the spatio-temporal distribution of terrestrial carbon fluxes for the time period of 1982 to 2002 simulated by a combination of the process-based dynamic global vegetation model LPJ and a 21-year time series of global AVHRR-fPAR data (fPAR – fraction of photosynthetically active radiation). Assimilation of the satellite data into the model allows improved simulations of carbon fluxes on global as well as on regional scales. As it is based on observed data and includes agricultural regions, the model combined with satellite data produces more realistic carbon fluxes of net primary production (NPP), soil respiration, carbon released by fire and the net land-atmosphere flux than the potential vegetation model. It also produces a good fit to the interannual variability of the CO2 growth rate. Compared to the original model, the model with satellite data constraint produces generally smaller carbon fluxes than the purely climate-based stand-alone simulation of potential natural vegetation, now comparing better to literature estimates. The lower net fluxes are a result of a combination of several effects: reduction in vegetation cover, consideration of human influence and agricultural areas, an improved seasonality, changes in vegetation distribution and species composition. This study presents a way to assess terrestrial carbon fluxes and elucidates the processes contributing to interannual variability of the terrestrial carbon exchange. Process-based terrestrial modelling and satellite-observed vegetation data are successfully combined to improve estimates of vegetation carbon fluxes and stocks. As net ecosystem exchange is the most interesting and most sensitive factor in carbon cycle modelling and highly uncertain, the presented results complementary contribute to the current knowledge, supporting the understanding of the terrestrial carbon budget.
Each organ of a multicellular organism is unique at the level of its tissues and cells. Furthermore, responses to environmental stimuli or developmental signals occur differentially at the single cell or tissue level. This underlines the necessity of precise investigation of the “building block of life” -the individual cell. Although recently large amount of data concerning different aspects of single cell performance was accumulated, our knowledge about development and differentiation of individual cell within specialized tissue are still far from being complete. To get more insight into processes that occur in certain individual cell during its development and differentiation changes in gene expression during life cycle of A. thaliana leaf hair cell (trichome) were explored in this work. After onset of trichome development this cell changes its cell cycle: it starts endoreduplication (a modified cell cycle in which DNA replication continues in the absence of mitosis and cytokinesis). This makes trichomes a suitable model for studying cell cycle regulation, regulation of cell development and differentiation. Cells of interest were sampled by puncturing them with glass microcapillaries. Each sample contained as few as ten single cells. At first time trichomes in initial stage of trichome development were investigated. To allow their sampling they were specifically labelled by green fluorescent protein (GFP). In total three cell types were explored: pavement cells, trichome initials and mature trichomes. Comparison of gene expression profiles of these cells allowed identification of the genes differentially expressed in subsequent stages of trichome development. Bioinformatic analysis of genes preferentially expressed in trichome initials showed their involvement in hormonal, metal, sulphur response and cell-cycle regulation. Expression pattern of three selected candidate genes, involved in hormonal response and early developmental processes was confirmed by independent method. Effects of mutations in these genes on both trichome and plant development as well as on plant metabolism were analysed. As an outcome of this work novel components in the sophisticated machinery of trichome development and cell cycle progression were identified. These factors could integrate hormone stimuli and network interactions between characterized and as yet unknown members of this machinery. I expect findings presented in this work to enhance and complement our current knowledge about cell cycle progression and trichome development, as well as about performance of the individual cell in general.
For more than 70 years, understanding of the mechanism of particle nucleation in emulsion polymerization has been one of the most challenging issues in heterophase polymerization research. Within this work a comprehensive experimental study of particle nucleation in emulsion polymerization of styrene at 70 °C and variety of conditions has been performed. To follow the onset of nucleation, on-line conductivity measurements were applied. This technique is highly sensitive to the mobility of conducting species and hence, it can be employed to follow aggregation processes leading to particle formation. On the other hand, by recording the optical transmission (turbidity) of the reaction mixture particle growth was followed. Complementary to the on-line investigations, off-line characterizations of the particle morphology and the molecular weight have been performed. The aim was to achieve a better insight in the processes taking place after starting the reaction via particle nucleation until formation of colloidally stable latex particles. With this experimental protocol the initial period of styrene emulsion polymerization in the absence as well as in the presence of various surfactants (concentrations above and below the critical micellization concentration) and also in the presence of seed particles has been investigated. Ionic and non-ionic initiators (hydrophilic and hydrophobic types) have been applied to start the polymerizations. Following the above algorithm, experimental evidence has been obtained showing the possibility of performing surfactant-free emulsion polymerization of styrene with oil-soluble initiators. The duration of the pre-nucleation period (that is the time between starting the polymerization and nucleation) can be precisely adjusted with the initiator hydrophobicity, the equilibration time of styrene in water, and the surfactant concentration. Spontaneous emulsification of monomer in water, as soon as both phases are brought into contact, is a key factor to explain the experimental results. The equilibration time of monomer in water as well as the type and concentration of other materials in water (surfactants, seed particles, etc.) control the formation rate and the size of the emulsified droplets and thus, have a strong influence on the particle nucleation and the particle morphology. One of the main tasks was to investigate the effect of surfactant molecules and especially micelles on the nucleation mechanism. Experimental results revealed that in the presence of emulsifier micelles the conductivity pattern does not change essentially. This means that the presence of emulsifiers does not change the mechanism of particle formation qualitatively. However, surfactants assist in the nucleation process as they lower the activation free energy of particle formation. Contrary, seed particles influence particle nucleation, substantially. In the presence of seed particles above a critical volume fraction the formation of new particles can be suppressed. However, micelles and seed particles as absorbers exhibit a common behavior under conditions where monomer equilibration is not allowed. Results prove that the nucleation mechanism comprises the initiation of water soluble oligomers in the aqueous phase followed by their aggregation. The process is heterogeneous in nature due to the presence of monomer droplets.
The interaction between neuronal cells can be identified as the computing mechanism of the brain. Neurons are complex cells that do not operate in isolation, but they are organized in a highly connected network structure. There is experimental evidence that groups of neurons dynamically synchronize their activity and process brain functions at all levels of complexity. A fundamental step to prove this hypothesis is to analyze large sets of single neurons recorded in parallel. Techniques to obtain these data are meanwhile available, but advancements are needed in the pre-processing of the large volumes of acquired data and in data analysis techniques. Major issues include extracting the signal of single neurons from the noisy recordings (referred to as spike sorting) and assessing the significance of the synchrony. This dissertation addresses these issues with two complementary strategies, both founded on the manipulation of point processes under rigorous analytical control. On the one hand I modeled the effect of spike sorting errors on correlated spike trains by corrupting them with realistic failures, and studied the corresponding impact on correlation analysis. The results show that correlations between multiple parallel spike trains are severely affected by spike sorting, especially by erroneously missing spikes. When this happens sorting strategies characterized by classifying only good'' spikes (conservative strategies) lead to less accurate results than tolerant'' strategies. On the other hand, I investigated the effectiveness of methods for assessing significance that create surrogate data by displacing spikes around their original position (referred to as dithering). I provide analytical expressions of the probability of coincidence detection after dithering. The effectiveness of spike dithering in creating surrogate data strongly depends on the dithering method and on the method of counting coincidences. Closed-form expressions and bounds are derived for the case where the dither equals the allowed coincidence interval. This work provides new insights into the methodologies of identifying synchrony in large-scale neuronal recordings, and of assessing its significance.
Atmospheric circulation and the surface mass balance in a regional climate model of Antarctica
(2007)
Understanding the Earth's climate system and particularly climate variability presents one of the most difficult and urgent challenges in science. The Antarctic plays a crucial role in the global climate system, since it is the principal region of radiative energy deficit and atmospheric cooling. An assessment of regional climate model HIRHAM is presented. The simulations are generated with the HIRHAM model, which is modified for Antarctic applications. With a horizontal resolution of 55km, the model has been run for the period 1958-1998 creating long-term simulations from initial and boundary conditions provided by the European Centre for Medium-Range Weather Forecasts (ECMWF) ERA40 re-analysis. The model output is compared with observations from observation stations, upper air data, global atmospheric analyses and satellite data. In comparison with the observations, the evaluation shows that the simulations with the HIRHAM model capture both the large and regional scale circulation features with generally small bias in the modeled variables. On the annual time scale the largest errors in the model simulations are the overestimation total cloud cover and the colder near-surface temperature over the interior of the Antarctic plateau. The low-level temperature inversion as well as low-level wind jet is well captured by the model. The decadal scale processes were studied based on trend calculations. The long-term run was divided into two 20 years parts. The 2m temperature, 500 hPa temperature, MSLP, precipitation and net mass balance trends were calculated for both periods and over 1958 - 1998. During the last two decades the strong surface cooling was observed over the Eastern Antarctica, this result is in good agreement with the result of Chapman and Walsh (2005) who calculated the temperature trend based on the observational data. The MSLP trend reveals a big disparity between the first and second parts of the 40 year run. The overall trend shows the strengthening of the circumpolar vortex and continental anticyclone. The net mass balance as well as precipitation show a positive trend over the Antarctic Peninsula region, along Wilkes Land and in Dronning Maud Land. The Antarctic ice sheet grows over the Eastern part of Antarctica with small exceptions in Dronning Maud Land and Wilkes Land and sinks in the Antarctic Peninsula; this result is in good agreement with the satellite-measured altitude presented in Davis (2005) . To better understand the horizontal structure of MSLP, temperature and net mass balance trends the influence of the Southern Annual Mode (SAM) on the Antarctic climate was investigated. The main meteorological parameters during the positive and negative Antarctic Oscillation (AAO) phases were compared to each other. A positive/negative AAO index means strengthening/weakening of the circumpolar vortex, poleward/northward storm tracks and prevailing/weakening westerly winds. For detailed investigation of global teleconnection, two positive and one negative periods of AAO phase were chosen. The differences in MSLP and 2m temperature between positive and negative AAO years during the winter months partly explain the surface cooling during the last decades.
Although educational content in electronic form is increasing dramatically, its usage in an educational environment is poor, mainly due to the fact that there is too much of (unreliable) redundant, and not relevant information. Finding appropriate answers is a rather difficult task being reliant on the user filtering of the pertinent information from the noise. Turning knowledge bases like the online tele-TASK archive into useful educational resources requires identifying correct, reliable, and "machine-understandable" information, as well as developing simple but efficient search tools with the ability to reason over this information. Our vision is to create an E-Librarian Service, which is able to retrieve multimedia resources from a knowledge base in a more efficient way than by browsing through an index, or by using a simple keyword search. In our E-Librarian Service, the user can enter his question in a very simple and human way; in natural language (NL). Our premise is that more pertinent results would be retrieved if the search engine understood the sense of the user's query. The returned results are then logical consequences of an inference rather than of keyword matchings. Our E-Librarian Service does not return the answer to the user's question, but it retrieves the most pertinent document(s), in which the user finds the answer to his/her question. Among all the documents that have some common information with the user query, our E-Librarian Service identifies the most pertinent match(es), keeping in mind that the user expects an exhaustive answer while preferring a concise answer with only little or no information overhead. Also, our E-Librarian Service always proposes a solution to the user, even if the system concludes that there is no exhaustive answer. Our E-Librarian Service was implemented prototypically in three different educational tools. A first prototype is CHESt (Computer History Expert System); it has a knowledge base with 300 multimedia clips that cover the main events in computer history. A second prototype is MatES (Mathematics Expert System); it has a knowledge base with 115 clips that cover the topic of fractions in mathematics for secondary school w.r.t. the official school programme. All clips were recorded mainly by pupils. The third and most advanced prototype is the "Lecture Butler's E-Librarain Service"; it has a Web service interface to respect a service oriented architecture (SOA), and was developed in the context of the Web-University project at the Hasso-Plattner-Institute (HPI). Two major experiments in an educational environment - at the Lycée Technique Esch/Alzette in Luxembourg - were made to test the pertinence and reliability of our E-Librarian Service as a complement to traditional courses. The first experiment (in 2005) was made with CHESt in different classes, and covered a single lesson. The second experiment (in 2006) covered a period of 6 weeks of intensive use of MatES in one class. There was no classical mathematics lesson where the teacher gave explanations, but the students had to learn in an autonomous and exploratory way. They had to ask questions to the E-Librarian Service just the way they would if there was a human teacher.
Stellar winds play an important role for the evolution of massive stars and their cosmic environment. Multiple lines of evidence, coming from spectroscopy, polarimetry, variability, stellar ejecta, and hydrodynamic modeling, suggest that stellar winds are non-stationary and inhomogeneous. This is referred to as 'wind clumping'. The urgent need to understand this phenomenon is boosted by its far-reaching implications. Most importantly, all techniques to derive empirical mass-loss rates are more or less corrupted by wind clumping. Consequently, mass-loss rates are extremely uncertain. Within their range of uncertainty, completely different scenarios for the evolution of massive stars are obtained. Settling these questions for Galactic OB, LBV and Wolf-Rayet stars is prerequisite to understanding stellar clusters and galaxies, or predicting the properties of first-generation stars. In order to develop a consistent picture and understanding of clumped stellar winds, an international workshop on 'Clumping in Hot Star Winds' was held in Potsdam, Germany, from 18. - 22. June 2007. About 60 participants, comprising almost all leading experts in the field, gathered for one week of extensive exchange and discussion. The Scientific Organizing Committee (SOC) included John Brown (Glasgow), Joseph Cassinelli (Madison), Paul Crowther (Sheffield), Alex Fullerton (Baltimore), Wolf-Rainer Hamann (Potsdam, chair), Anthony Moffat (Montreal), Stan Owocki (Newark), and Joachim Puls (Munich). These proceedings contain the invited and contributed talks presented at the workshop, and document the extensive discussions.
Electron transfer phenomena in proteins represent one of the most common types of biochemical reactions. They play a central role in energy conversion pathways in living cells, and are crucial components in respiration and photosynthesis. These complex biochemical reaction cascades consist of a series of proteins and protein complexes that couple a charge transfer to different forms of chemical energy. The efficiency and sophisticated optimisation of signal transfer in these natural redox chains has inspired engineering of artificial architectures mimicking essential properties of their natural analogues. Implementation of direct electron transfer (DET) in protein assemblies was a breakthrough in bioelectronics, providing a simple and efficient way for coupling biological recognition events to a signal transducer. DET avoids the use of redox mediators, reducing potential interferences and side reactions, as well as being more compatible with in vivo conditions. However, only a few haem proteins, including the redox protein cytochrome c (cyt.c), and blue copper enzymes show efficient DET on different kinds of electrodes. Previous investigations with cyt.c have mainly focused on heterogeneous electron transfer of monolayers of this protein on gold. An important advance was the fabrication of cyt.c multilayers by electrostatic layer-by-layer self-assembly. The ease of fabrication, the stability, and the controllable permeability of polyelectrolyte multilayers have made them particularly attractive for electroanalytical applications. With cyt.c and sulfonated polyaniline it was for the first time possible that fully electro-active multilayers of the redox protein could be prepared. This approach was extended to design an analytical signal chain based on multilayers of cyt.c and xanthine oxidase (XOD). The system does not need an external mediator but relies on an in situ generation of a mediating radical and thus allows a signal transfer from hypoxanthine via the substrate converting enzyme and cyt.c to the electrode. Another kind of a signal chain is based on assembling proteins in complexes on electrodes in such a way that a direct protein-protein electron transfer becomes feasible. This design does not need a redox mediator in analogy to natural protein communication. For this purpose, cyt.c and the enzyme bilirubin oxidase (BOD, EC 1.3.3.5) are co-immobilized in a self-assembled polyelectrolyte multilayer on gold electrodes. Although these two proteins are not natural reaction partners, the protein architecture facilitates an electron transfer from the electrode via multiple protein layers to molecular oxygen resulting in a significant catalytic reduction current. Finally, we describe a novel strategy for multi-protein layer-by-layer self-assembly combining cyt.c with an enzyme sulfite oxidase (SOx) without use of any additional polymer. Electrostatic interactions between these two proteins with rather separated pI values during the assembly process from a low ionic strength buffer were found sufficient for the layer-by-layer deposition of the both biomolecules. It is anticipated that the concepts described in this work will stimulate further progress in multilayer design of even more complex biomimetic signal cascades taking advantage of direct communication between proteins.
The objective of this thesis is to improve the knowledge of control mechanisms of hydrological induced mass movements. To this end, detailed hydrological process studies and physically-based hydrological modelling were applied. The study site is a hillslope in the Dornbirn Ache valley near Bregenz, Austria. This so called Heumös slope features a deep-seated translational shear zone and surface near creep movements of up to 10 cm a year. The Cretaceous marlstones of the Austrian Helveticum have a high susceptibility for weathering and might form clay-rich cohesive sediments. In addition, glacial and post-glacial processes formed an unstable hillslope. High yearly precipitation depths of about 2100 mm and rainstorms with both high intensities and precipitation depths govern surface and subsurface hydrological processes. Pressure propagation induced in hydrological active areas influences laterally the groundwater reactions of the moving mass. A complex three-dimensional subsurface pressure system is the cause for fast groundwater reactions despite low hydraulic conductivities. To understand hillslope scale variability, hydrotopes representing specific dominating processes were mapped using vegetation association distribution and soil core analysis. Detailed small-scale soil investigations followed to refine the understanding of these hydrotopes. A perceptional model was developed from the hydrotope distribution and was corroborated by these detailed investigations. The moving hillslope is dominated by surface-runoff generation. Infiltration and deep percolation of water is inhibited through clay-rich gleysols; the yearly average soil moisture is close to saturation. Steep slopes adjacent to the moving hillslope are far more active concerning infiltration, preferential flow and groundwater fluctuations. Spring discharge observations at the toe of the steep slopes are in close relation to groundwater table observations on the moving hillslope body. Evidence of pressure propagation from the steep slopes towards the hillslope body is gathered by comparison of dominating structures and processes. The application of the physically-based hydrological model CATFLOW substantiates the idea of pressure propagation as a key process for groundwater reactions and as a possible trigger for movement in the hillslope.
Nature has always served as a model for mimicking and inspiration to humans in their efforts to improve their life. Researchers have been inspired by nature to produce biomimetic materials with molecular recognition properties by design rather than evolution. Molecular imprinting is one way to prepare such materials. Such smart materials with new functionalities are at the forefront of the development of a relevant number of ongoing and perspective applications ranging from consumer to space industry. Molecularly imprinted polymers were developed by mimicking the natural enzymes or antibodies that serve as host for binding target molecules. These imprints were used as a recognition element to substitute natural biomolecules in biosensors. The concept behind molecular imprinting is to mold a material (with the desired chemical properties) around individual molecules. Upon removal of the molecular templates, one is left with regions in the molded material that fit the shape of the template molecules. Thus, molecular imprinting results in materials that can selectively bind to molecules of interest. Imprinted materials resulted in applications ranging from chemical separation to bioanalytics. In this work attempts were made particularly in the development of molecularly imprinted polymer based thermometric sensors. The main effort was focused towards the development of an covalently imprinted polymer that would be able to selectively bind fructosyl valine (Fru-Val), the N-terminal constituent of hemoglobin A1c ß-chains. Taking into account the known advantages of imprinted polymers, e.g. robustness, thermal and chemical stability, imprinted materials were successfully used as a recognition element in the sensor. One of the serious problems associated with the development of MIP sensors and which lies in the absence of a generic procedure for the transformation of the polymer-template binding event into a detectable signal has been addressed by developing the "thermometric" approach. In general the developed approach gives a new insight on MIP/Analyte interactions.
Orbits of charged particles under the effect of a magnetic field are mathematically described by magnetic geodesics. They appear as solutions to a system of (nonlinear) ordinary differential equations of second order. But we are only interested in periodic solutions. To this end, we study the corresponding system of (nonlinear) parabolic equations for closed magnetic geodesics and, as a main result, eventually prove the existence of long time solutions. As generalization one can consider a system of elliptic nonlinear partial differential equations whose solutions describe the orbits of closed p-branes under the effect of a "generalized physical force". For the corresponding evolution equation, which is a system of parabolic nonlinear partial differential equations associated to the elliptic PDE, we can establish existence of short time solutions.
Functional analysis of selected DOF transcription factors in the model plant Arabidopsis thaliana
(2007)
Transcription factors (TFs) are global regulators of gene expression playing essential roles in almost all biological processes, and are therefore of great scientific and biotechnological interest. This project focused on functional characterisation of three DNA-binding-with-one-zinc-finger (DOF) TFs from the genetic model plant Arabidopsis thaliana, namely OBP1, OBP2 and AtDOF4;2. These genes were selected due to severe growth phenotypes conferred upon their constitutive over-expression. To identify biological processes regulated by OBP1, OBP2 and AtDOF4;2 in detail molecular and physiological characterization of transgenic plants with modified levels of OBP1, OBP2 and AtDOF4;2 expression (constitutive and inducible over-expression, RNAi) was performed using both targeted and profiling technologies. Additionally expression patterns of studied TFs and their target genes were analyzed using promoter-GUS lines and publicly available microarray data. Finally selected target genes were confirmed by chromatin immuno-precipitation and electrophoretic-mobility shift assays. This combinatorial approach revealed distinct biological functions of OBP1, OBP2 and AtDOF4;2. Specifically OBP2 controls indole glucosinolate / auxin homeostasis by directly regulating the enzyme at the branch of these pathways; CYP83B1 (Skirycz et al., 2006). Glucosinolates are secondary compounds important for defence against herbivores and pathogens in the plants order Caparales (e.g. Arabidopsis, canola and broccoli) whilst auxin is an essential plant hormone. Hence OBP2 is important for both response to biotic stress and plant growth. Similarly to OBP2 also AtDOF4;2 is involved in the regulation of plant secondary metabolism and affects production of various phenylpropanoid compounds in a tissue and environmental specific manner. It was found that under certain stress conditions AtDOF4;2 negatively regulates flavonoid biosynthetic genes whilst in certain tissues it activates hydroxycinnamic acid production. It was hypothesized that this dual function is most likely related to specific interactions with other proteins; perhaps other TFs (Skirycz et al., 2007). Finally OBP1 regulates both cell proliferation and cell expansion. It was shown that OBP1 controls cell cycle activity by directly targeting the expression of core cell cycle genes (CYCD3;3 and KRP7), other TFs and components of the replication machinery. Evidence for OBP1 mediated activation of cell cycle during embryogenesis and germination will be presented. Additionally and independently on its effects on cell proliferation OBP1 negatively affects cell expansion via reduced expression of cell wall loosening enzymes. Summing up this work provides an important input into our knowledge on DOF TFs function. Future work will concentrate on establishing exact regulatory networks of OBP1, OBP2 and AtDOF4;2 and their possible biotechnological applications.
Chitooligosaccharides are composed of linear β-(1→4)-linked 2-acetamido-2-deoxy-β-D-glucopyranose (GlcNAc) and/or 2-amino-2-deoxy-β-D-glucopyranose (GlcN). They are of interest due to their remarkable biological properties including antibacterial, antitumor, antifungal and elicitor activities. They can be obtained from the aminoglucan chitosan by chemical or enzymatic degradation which obviously affords rather heterogenous mixtures. On the other hand, chemical synthesis provides pure compounds with defined sequences of GlcNAc and GlcN monomers. The synthesis of homo- and hetero-chitobioses and hetero-chitotetraoses is described in this thesis. Dimethylmaleoyl and phthaloyl groups were used for protection of the amines. The donor was activated as the trichloroacetimidate in order to form the β-linkages. Glycosylation in the presence of trimethylsilyl trifluoromethanesulfonate, followed by N- and O-deprotection furnished chitobioses and chitotetraoses in good yields.
Giacconi et al. (1962) discovered a diffuse cosmic X-ray background with rocket experiments when they searched for lunar X-ray emission. Later satellite missions found a spectral peak in the cosmic X-ray background at ~30 keV. Imaging X-ray satellites such as ROSAT (1990-1999) were able to resolve up to 80% of the background below 2 keV into single point sources, mainly active galaxies. The cosmic X-ray background is the integration of all accreting super-massive (several million solar masses) black holes in the centre of active galaxies over cosmic time. Synthesis models need further populations of X-ray absorbed active galaxy nuclei (AGN) in order to explain the cosmic X-ray background peak at ~30 keV. Current X-ray missions such as XMM-Newton and Chandra offer the possibility of studying these additional populations. This Ph.D. thesis studies the populations that dominate the X-ray sky. For this purpose the 120 ksec XMM-Newton Marano field survey, named for an earlier optical quasar survey in the southern hemisphere, is analysed. Based on the optical follow-up observations the X-ray sources are spectroscopically classified. Optical and X-ray properties of the different X-ray source populations are studied and differences are derived. The amount of absorption in the X-ray spectra of type II AGN, which are considered as a main contributor to the X-ray background at ~30 keV, is determined. In order to extend the sample size of the rare type II AGN, this study also includes objects from another survey, the XMM-Newton Serendipitous Medium Sample. In addition, the dependence of the absorption in type II AGN with redshift and X-ray luminosity is analysed. We detected 328 X-ray sources in the Marano field. 140 sources were spectroscopically classified. We found 89 type I AGN, 36 type II AGN, 6 galaxies, and 9 stars. AGN, galaxies, and stars are clearly distinguishable by their optical and X-ray properties. Type I and II AGN do not separate clearly. They have a significant overlap in all studied properties. In a few cases the X-ray properties are in contradiction to the observed optical properties for type I and type II AGN. For example we find type II AGN that show evidence for optical absorption but are not absorbed in X-rays. Based on the additional use of near infra-red imaging (K-band), we were able to identify several of the rare type II AGN. The X-ray spectra of type II AGN from the XMM-Newton Marano field survey and the XMM-Newton Serendipitous Medium Sample were analysed. Since most of the sources have only ~40 X-ray counts in the XMM-Newton PN-detector, I carefully studied the fit results of simulated X-ray spectra as a function of fit statistic and binning method. The objects revealed only moderate absorption. In particular, I do not find any Compton-thick sources (absorbed by column densities of NH > 1.5 x 10^24 cm^−2). This gives evidence that type II AGN are not the main contributor of the X-ray background around 30 keV. Although bias effects may occur, type II AGN show no noticeable trend of the amount of absorption with redshift or X-ray luminosity.
Streamflow dynamics in mountainous environments are controlled by runoff generation processes in the basin upstream. Runoff generation processes are thus a major control of the terrestrial part of the water cycle, influencing both, water quality and water quantity as well as their dynamics. The understanding of these processes becomes especially important for the prediction of floods, erosion, and dangerous mass movements, in particular as hydrological systems often show threshold behavior. In case of extensive environmental changes, be it in climate or in landuse, the understanding of runoff generation processes will allow us to better anticipate the consequences and can thus lead to a more responsible management of resources as well as risks. In this study the runoff generation processes in a small undisturbed catchment in the Chilean Andes were investigated. The research area is characterized by steep hillslopes, volcanic ash soils, undisturbed old growth forest and high rainfall amounts. The investigation of runoff generation processes in this data scarce area is of special interest as a) little is known on the hydrological functioning of the young volcanic ash soils, which are characterized by extremely high porosities and hydraulic conductivities, b) no process studies have been carried out in this area at either slope or catchment scale, and c) understanding the hydrological processes in undisturbed catchments will provide a basis to improve our understanding of disturbed systems, the shift in processes that followed the disturbance and maybe also future process evolution necessary for the achievement of a new steady state. The here studied catchment has thus the potential to serve as a reference catchment for future investigations. As no long term data of rainfall and runoff exists, it was necessary to replace long time series of data with a multitude of experimental methods, using the so called "multi-method approach". These methods cover as many aspects of runoff generation as possible and include not only the measurement of time series such as discharge, rainfall, soil water dynamics and groundwater dynamics, but also various short term measurements and experiments such as determination of throughfall amounts and variability, water chemistry, soil physical parameters, soil mineralogy, geo-electrical soundings and tracer techniques. Assembling the results like pieces of a puzzle produces a maybe not complete but nevertheless useful picture of the dynamic ensemble of runoff generation processes in this catchment. The employed methods were then evaluated for their usefulness vs. expenditures (labour and financial costs). Finally, the hypotheses - the perceptual model of runoff generation generated from the experimental findings - were tested with the physically based model Catflow. Additionally the process-based model Wasim-ETH was used to investigate the influence of landuse on runoff generation at the catchment scale. An initial assessment of hydrologic response of the catchment was achieved with a linear statistical model for the prediction of event runoff coefficients. The parameters identified as best predictors give a first indication of important processes. Various results acquired with the "multi-method approach" show that response to rainfall is generally fast. Preferential vertical flow is of major importance and is reinforced by hydrophobicity during the summer months. Rapid lateral water transport is necessary to produce the fast response signal, however, while lateral subsurface flow was observed at several soil moisture profiles, the location and type of structures causing fast lateral flow on the hillslope scale is still not clear and needs to be investigated in more detail. Surface runoff has not been observed and is unlikely due to the high hydraulic conductivities of the volcanic ash soils. Additionally, a large subsurface storage retains most of the incident rainfall amount during events (>90%, often even >95%) and produces streamflow even after several weeks of drought. Several findings suggest a shift in processes from summer to winter causing changes in flow patterns, changes in response of stream chemistry to rainfall events and also in groundwater-surface water interactions. The results of the modelling study confirm the importance of rapid and preferential flow processes. However, due to the limited knowledge on subsurface structures the model still does not fully capture runoff response. Investigating the importance of landuse on runoff generation showed that while peak runoff generally increased with deforested area, the location of these areas also had an effect. Overall, the "multi-method approach" of replacing long time series with a multitude of experimental methods was successful in the identification of dominant hydrological processes and thus proved its applicability for data scarce catchments under the constraint of limited resources.
Writing an alternative Australia : women and national discourse in nineteenth-century literature
(2007)
In this thesis, I want to outline the emergence of the Australian national identity in colonial Australia. National identity is not a politically determined construct but culturally produced through discourse on literary works by female and male writers. The emergence of the dominant bushman myth exhibited enormous strength and influence on subsequent generations and infused the notion of “Australianness” with exclusively male characteristics. It provided a unique geographical space, the bush, on and against which the colonial subject could model his identity. Its dominance rendered non-male and non-bush experiences of Australia as “un-Australian.” I will present a variety of contemporary voices – postcolonial, Aboriginal, feminist, cultural critics – which see the Australian identity as a prominent topic, not only in the academia but also in everyday culture and politics. Although positioned in different disciplines and influenced by varying histories, these voices share a similar view on Australian society: Australia is a plural society, it is home to millions of different people – women, men, and children, Aboriginal Australians and immigrants, newly arrived and descendents of the first settlers – with millions of different identities which make up one nation. One version of national identity does not account for the multitude of experiences; one version, if applied strictly, renders some voices unheard and oppressed. After exemplifying how the literature of the 1890s and its subsequent criticism constructed the itinerant worker as “the” Australian, literary productions by women will be singled out to counteract the dominant version by presenting different opinions on the state of colonial Australia. The writers Louisa Lawson, Barbara Baynton, and Tasma are discussed with regard to their assessment of their mother country. These women did not only present a different picture, they were also gifted writers and lived the ideal of the “New Women:” they obtained divorces, remarried, were politically active, worked for their living and led independent lives. They paved the way for many Australian women to come. In their literary works they allowed for a dual approach to the bush and the Australian nation. Louisa Lawson credited the bushwoman with heroic traits and described the bush as both cruel and full of opportunities not known to women in England. She understood women’s position in Australian society as oppressed and tried to change politics and culture through the writings in her feminist magazine the Dawn and her courageous campaign for women suffrage. Barbara Baynton painted a gloomy picture of the Australian bush and its inhabitants and offered one of the fiercest critiques of bush society. Although the woman is presented as the able and resourceful bushperson, she does not manage to survive in an environment which functions on male rules and only values the economic potential of the individual. Finally, Tasma does not present as outright a critique as Barbara Baynton, however, she also attests the colonies a fascination with wealth which she renders questionable. She offers an informed judgement on colonial developments in the urban surrounds of the city of Melbourne through the comparison of colonial society with the mother country England. Tasma attests that the colonies had a fascination with wealth which she renders questionable. She offers an informed judgement on colonial developments in the urban surrounds of the city of Melbourne through the comparison of colonial society with the mother country England and demonstrates how uncertainties and irritations emerged in the course of Australia’s nation formation. These three women, as writers, commentators, and political activists, faced exclusion from the dominant literary discourses. Their assessment of colonial society remained unheard for a long time. Now, after much academic excavation, these voices speak to us from the past and remind us that people are diverse, thus nation is diverse. Dominant power structures, the institutions and individuals who decide who can contribute to the discourse on nation, have to be questioned and reassessed, for they mute voices which contribute to a wider, to the “full”, and maybe “real” picture of society.
In this work, some new results to exploit the recurrence properties of quasiperiodic dynamical systems are presented by means of a two dimensional visualization technique, Recurrence Plots(RPs). Quasiperiodicity is the simplest form of dynamics exhibiting nontrivial recurrences, which are common in many nonlinear systems. The concept of recurrence was introduced to study the restricted three body problem and it is very useful for the characterization of nonlinear systems. I have analyzed in detail the recurrence patterns of systems with quasiperiodic dynamics both analytically and numerically. Based on a theoretical analysis, I have proposed a new procedure to distinguish quasiperiodic dynamics from chaos. This algorithm is particular useful in the analysis of short time series. Furthermore, this approach demonstrates to be efficient in recognizing regular and chaotic trajectories of dynamical systems with mixed phase space. Regarding the application to real situations, I have shown the capability and validity of this method by analyzing time series from fluid experiments.
As land-cover conversion continues to expand into ever more remote areas in the humid tropics, montane rainforests are increasingly threatened. In the south Ecuadorian Andes, they are not only subject to man-made disturbances but also to naturally occurring landslides. I was interested in the impact of this ecosystem dynamics on a key parameter of the hydrologic cycle, the soil saturated hydraulic conductivity (synonym: permeability; Ks from here on), because it is a sensitive indicator for soil disturbances. My general objective was to quantify the effects of the regional natural and human disturbances on the saturated hydraulic conductivity and to describe the resulting spatial-temporal patterns. The main hypotheses were: 1) disturbances cause an apparent displacement of the less permeable soil layer towards the surface, either due to a loss of the permeable surface soil after land-sliding, or as a consequence of the surface soil compaction under cattle pastures; 2) ‘recovery’ from disturbance, either because of landslide re-vegetation or because of secondary succession after pasture abandonment, involves an apparent displacement of the less permeable layer back towards the original depth an 3) disturbances cause a simplification of the Ks spatial structure, i.e. the spatially dependent random variation diminishes; the subsequent recovery entails the re-establishment of the original structure. In my first study, I developed a synthesis of recent geostatistical research regarding its applicability to soil hydraulic data, including exploratory data analysis and variogram estimation techniques; I subsequently evaluated the results in terms of spatial prediction uncertainty. Concerning the exploratory data analysis, my main results were: 1) Gaussian uni- and bivariate distributions of the log-transformed data; 2) the existence of significant local trends; 3) no need for robust estimation; 4) no anisotropic variation. I found partly considerable differences in covariance parameters resulting from different variogram estimation techniques, which, in the framework of spatial prediction, were mainly reflected in the spatial connectivity of the Ks-field. Ignoring the trend component and an arbitrary use of robust estimators, however, would have the most severe consequences in this respect. Regarding variogram modeling, I encouraged restricted maximum likelihood estimation because of its accuracy and independence on the selected lags needed for experimental variograms. The second study dealt with the Ks spatial-temporal pattern in the sequences of natural and man-made disturbances characteristic for the montane rainforest study area. To investigate the disturbance effects both on global means and the spatial structure of Ks, a combined design-and model-based sampling approach was used for field-measurements at soil depths of 12.5, 20, and 50 cm (n=30-150/depth) under landslides of different ages (2 and 8 years), under actively grazed pasture, fallows following pasture abandonment (2 to 25 years of age), and under natural forest. Concerning global means, our main findings were 1) global means of the soil permeability generally decrease with increasing soil depth; 2) no significant Ks differences can be observed among landslides and compared to the natural forest; 3) a distinct permeability decrease of two orders of magnitude occurs after forest conversion to pasture at shallow soil depths, and 4) the slow regeneration process after pasture abandonment requires at least one decade. Regarding the Ks spatial structure, we found that 1) disturbances affect the Ks spatial structure in the topsoil, and 2) the largest differences in spatial patterns are associated with the subsoil permeability. In summary, the regional landslide activity seems to affect soil hydrology to a marginal extend only, which is in contrast to the pronounced drop of Ks after forest conversion. We used this spatial-temporal information combined with local rain intensities to assess the partitioning of rainfall into vertical and lateral flowpaths under undisturbed, disturbed, and regenerating land-cover types in the third study. It turned out that 1) the montane rainforest is characterized by prevailing vertical flowpaths in the topsoil, which can switch to lateral directions below 20 cm depth for a small number of rain events, which may, however, transport a high portion of the annual runoff; 2) similar hydrological flowpaths occur under the landslides except for a somewhat higher probability of impermeable layer formation in the topsoil of a young landslide, and 3) pronounced differences in runoff components can be observed for the human disturbance sequence involving the development of near-surface impeding layers for 24, 44, and 8 % of rain events for pasture, a two-year-old fallow, and a ten-year-old fallow, respectively.
Today about 24 Million people worldwide suffer from dementia, Alzheimer’s Disease accounts for approximately 50-60% of all dementia cases. As the prevalence of dementia grows with increasing age Alzheimer’s Disease becomes more and more of an issue for society as the proportion of elderly people increases from year to year. It is well established, that the amino acid glutamate - quantitatively being the most important neurotransmitter in the central nervous system (CNS) - may reach toxic concentrations if not cleared from the synaptic cleft into which it is released during transmittance of action potentials. In Alzheimer’s Disease there is strong evidence for a generally impaired glutamate uptake system which in turn is thought to result in toxic levels of the amino acid with the potential to kill off neurons. The excitatory amino acid transporter 1 (EAAT1) belongs to the family of Na+-dependent glutamate transporter and accounts together with EAAT2 for most of the glutamate uptake in the CNS. In this project a new splice variant of EAAT1, skipping exon 3 was detected in human brain samples and subsequently called EAAT1Δ3, this being the second splice variant found after the recent detection of EAAT1Δ9. A method was developed to quantify the transcript of EAAT1 wt, EAAT1Δ3 and EAAT1Δ9 by means of real-time PCR. Samples were taken from different brain areas of a set of control and AD cases. The areas chosen for examination are affected differently in Alzheimer’s Disease, this was used an internal control for the experiments done in this project as to determine whether any effect observed is specific for AD, i.e. AD affected areas or is generally seen in all areas examined. The results of this project show that EAAT1Δ3 is transcribed in very low copy numbers making up a proportion of 0.15% of EAAT1 wt whereas EAAT1Δ9 is transcribed in a considerably large proportion of EAAT1 wt of 26.6%. It was moreover found that all EAAT1 variants are transcribed at significantly lower rates (P<0.0001) in AD cases, supporting the theory that EAAT1 protein expression is reduced to a point where glutamate uptake normally mediated by this transporter is impaired. This in turn is thought to result in toxic levels glutamate accounting for neuronal loss in the disease. No area-dependent effects were found, suggesting that the reduction of EAAT1 transcription is rather a result of an underlying general mechanism present in AD. Further research will have to be done to assess the degree of EAAT1 expression in AD and whether those future findings match with the result of this project.