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Recently, several faint ringlets in the Saturnian ring system were found to maintain a peculiar orientation relative to Sun. The Encke gap ringlets as well as the ringlet in the outer rift of the Cassini division were found to have distinct spatial displacements of several tens of kilometers away from Saturn towards Sun, referred to as heliotropicity (Hedman et al., 2007). This is quite exceptional, since dynamically one would expect eccentric features in the Saturnian rings to precess around Saturn over periods of months. In our study we address this exceptional behavior by investigating the dynamics of circumplanetary dust particles with sizes in the range of 1-100 µm. These small particles are perturbed by non-gravitational forces, in particular, solar radiation pres- sure, Lorentz force, and planetary oblateness, on time-scales of the order of days. The combined influences of these forces cause periodical evolutions of grains’ orbital ec- centricities as well as precession of their pericenters, which can be shown by secular perturbation theory. We show that this interaction results in a stationary eccentric ringlet, oriented with its apocenter towards the Sun, which is consistent with obser- vational findings. By applying this heliotropic dynamics to the central Encke gap ringlet, we can give a limit for the expected smallest grain size in the ringlet of about 8.7 microns, and constrain the minimal lifetime to lie in the order of months. Furthermore, our model matches fairly well the observed ringlet eccentricity in the Encke gap, which supports recent estimates on the size distribution of the ringlet material (Hedman et al., 2007). The ringlet-width however, that results from our modeling based on heliotropic dynamics, slightly overestimates the observed confined ringlet-width by a factor of 3 to 10, depending on the width-measure being used. This is indicative for mechanisms, not included in the heliotropic model, which potentially confine the ringlet to its observed width, including shepherding and scattering by embedded moonlets in the ringlet region. Based on these results, early investigations (Cuzzi et al., 1984, Spahn and Wiebicke, 1989, Spahn and Sponholz, 1989), and recent work that has been published on the F ring (Murray et al., 2008) - to which the Encke gap ringlets are found to share similar morphological structures - we model the maintenance of the central ringlet by embedded moonlets. These moonlets, believed to have sizes of hundreds of meters across, release material into space, which is eroded by micrometeoroid bombardment (Divine, 1993). We further argue that Pan - one of Saturn’s moons, which shares its orbit with the central ringlet of the Encke gap - is a rather weak source of ringlet material that efficiently confines the ringlet sources (moonlets) to move on horseshoe-like orbits. Moreover, we suppose that most of the narrow heliotropic ringlets are fed by a moonlet population, which is held together by the largest member to move on horseshoe-like orbits. Modeling the equilibrium between particle source and sinks with a primitive balance equation based on photometric observations (Porco et al., 2005), we find the minimal effective source mass of the order of 3 · 10-2MPan, which is needed to keep the central ringlet from disappearing.
Proteins are chain molecules built from amino acids. The precise sequence of the 20 different types of amino acids in a protein chain defines into which structure a protein folds, and the three-dimensional structure in turn specifies the biological function of the protein. The reliable folding of proteins is a prerequisite for their robust function. Misfolding can lead to protein aggregates that cause severe diseases, such as Alzheimer's, Parkinson's, or the variant Creutzfeldt-Jakob disease. Small single-domain proteins often fold without experimentally detectable metastable intermediate states. The folding dynamics of these proteins is thought to be governed by a single transition-state barrier between the unfolded and the folded state. The transition state is highly instable and cannot be observed directly. However, mutations in which a single amino acid of the protein is substituted by another one can provide indirect access. The mutations slightly change the transition-state barrier and, thus, the folding and unfolding times of the protein. The central question is how to reconstruct the transition state from the observed changes in folding times. In this habilitation thesis, a novel method to extract structural information on transition states from mutational data is presented. The method is based on (i) the cooperativity of structural elements such as alpha-helices and beta-hairpins, and (ii) on splitting up mutation-induced free-energy changes into components for these elements. By fitting few parameters, the method reveals the degree of structure formation of alpha-helices and beta-hairpins in the transition state. In addition, it is shown in this thesis that the folding routes of small single-domain proteins are dominated by loop-closure dependencies between the structural elements.
The paper sheds some light on the education returns in Germany in the post war period. After describing higher education in Germany the current stand of higher education financing within the single states is presented. In six states tuition fees will be introduced in 2007/08 and discussions are going on in even some more. In the second part of the paper an empirical analysis is done using longitudinal data from the German social pension system. The analysis over the whole lifecycle renders results which proof that the higher education advantages are quite remarkable and might be a justification for more intensified financing by tuition fees. But all this has to be embedded into an encompassing strategy of tax and social policy, especially to prevent a strengthened process of social selection, which would be counterproductive for an increased and highly qualified human capital in Germany.
Understanding the interactions of predators and their prey and their responses to environmental changes is one of the striking features of ecological research. In this thesis, spring dynamics of phytoplankton and its consumers, zooplankton, were considered in dependence on the environmental conditions in a deep lake (Lake Constance) and a shallow marine water (mesocosms from Kiel Bight), using descriptive statistics, multiple regression models, and process-oriented dynamic simulation models. The development of the spring phytoplankton bloom, representing a dominant feature in the plankton dynamics in temperate and cold oceans and lakes, may depend on temperature, light, and mixing intensity, and the success of over-wintering phyto- and zooplankton. These factors are often correlated in the field. Unexpectedly, irradiance often dominated algal net growth rather than vertical mixing even in deep Lake Constance. Algal net losses from the euphotic layer to larger depth were induced by vertical mixing, but were compensated by the input from larger depth when algae were uniformly distributed over the water column. Dynamics of small, fast-growing algae were well predicted by abiotic variables, such as surface irradiance, vertical mixing intensity, and temperature. A simulation model additionally revealed that even in late winter, grazing may represent an important loss factor of phytoplankton during calm periods when losses due to mixing are small. The importance of losses by mixing and grazing changed rapidly as it depended on the variable mixing intensity. Higher temperature, lower global irradiance and enhanced mixing generated lower algal biomass and primary production in the dynamic simulation model. This suggests that potential consequences of climate change may partly counteract each other. The negative effect of higher temperatures on phytoplankton biomass was due to enhanced temperature-sensitive grazing losses. Comparing the results from deep Lake Constance to those of the shallow mesocosm experiments and simulations, confirmed the strong direct effect of light in contrast to temperature, and the importance of grazing already in early spring as soon as moderate algal biomasses developed. In Lake Constance, ciliates dominated the herbivorous zooplankton in spring. The start of ciliate net growth in spring was closely linked to that of edible algae, chlorophyll a and the vertical mixing intensity but independent of water temperature. The duration of ciliate dominance in spring was largely controlled by the highly variable onset of the phytoplankton bloom, and little by the less variable termination of the ciliate bloom by grazing of meta-zooplankton. During years with an extended spring bloom of algae and ciliates, they coexisted at relatively high biomasses over 15-30 generations, and internally forced species shifts were observed in both communities. Interception feeders alternated with filter feeders, and cryptomonads with non-cryptomonads in their relative importance. These dynamics were not captured by classical 1-predator-1-prey models which consistently predict pronounced predator-prey cycles or equilibria with either the predator or the prey dominating or suppressed. A multi-species predator-prey model with predator species differing in their food selectivity, and prey species in their edibility reproduced the observed patterns. Food-selectivity and edibility were related to the feeding and growth characteristics of the species, which represented ecological trade-offs. For example, the prey species with the highest edibility also had the highest maximum growth rate. Data and model revealed endogenous driven ongoing species alternations, which yielded a higher variability in species-specific biomasses than in total predator and prey biomass. This holds for a broad parameter space as long as the species differ functionally. A more sophisticated model approach enabled the simulation of a continuum of different functional types and adaptability of predator and prey communities to altered environmental conditions, and the maintenance of a rather low model complexity, i.e., low number of equations and free parameters. The community compositions were described by mean functional traits --- prey edibility and predator food-selectivity --- and their variances. The latter represent the functional diversity of the communities and thus, the potential for adaptation. Oscillations in the mean community trait values indicated species shifts. The community traits were related to growth and grazing characteristics representing similar trade-offs as in the multi-species model. The model reproduced the observed patterns, when nonlinear relationships between edibility and capacity, and edibility and food availability for the predator were chosen. A constant minimum amount of variance represented ongoing species invasions and thus, preserved a diversity which allows adaptation on a realistic time-span.
Plants are the primary producers of biomass and thereby the basis of all life. Many varieties are cultivated, mainly to produce food, but to an increasing amount as a source of renewable energy. Because of the limited acreage available, further improvements of cultivated species both with respect to yield and composition are inevitable. One approach to further progress in developing improved plant cultivars is a systems biology oriented approach. This work aimed to investigate the primary metabolism of the model plant A.thaliana and its relation to plant growth using quantitative genetics methods. A special focus was set on the characterization of heterosis, the deviation of hybrids from their parental means for certain traits, on a metabolic level. More than 2000 samples of recombinant inbred lines (RILs) and introgression lines (ILs) developed from the two accessions Col-0 and C24 were analyzed for 181 metabolic traces using gas-chromatography/ mass-spectrometry (GC-MS). The observed variance allowed the detection of 157 metabolic quantitative trait loci (mQTL), genetic regions carrying genes, which are relevant for metabolite abundance. By analyzing several hundred test crosses of RILs and ILs it was further possible to identify 385 heterotic metabolic QTL (hmQTL). Within the scope of this work a robust method for large scale GC-MS analyses was developed. A highly significant canonical correlation between biomass and metabolic profiles (r = 0.73) was found. A comparable analysis of the results of the two independent experiments using RILs and ILs showed a large agreement. The confirmation rate for RIL QTL in ILs was 56 % and 23 % for mQTL and hmQTL respectively. Candidate genes from available databases could be identified for 67 % of the mQTL. To validate some of these candidates, eight genes were re-sequenced and in total 23 polymorphisms could be found. In the hybrids, heterosis is small for most metabolites (< 20%). Heterotic QTL gave rise to less candidate genes and a lower overlap between both populations than was determined for mQTL. This hints that regulatory loci and epistatic effects contribute to metabolite heterosis. The data described in this thesis present a rich source for further investigation and annotation of relevant genes and may pave the way towards a better understanding of plant biology on a system level.
The selective infrared (IR) excitation of molecular vibrations is a powerful tool to control the photoreactivity prior to electronic excitation in the ultraviolet / visible (UV/Vis) light regime ("vibrationally mediated chemistry"). For adsorbates on surfaces it has been theoretically predicted that IR preexcitation will lead to higher UV/Vis photodesorption yields and larger cross sections for other photoreactions. In a recent experiment, IR-mediated desorption of molecular hydrogen from a Si(111) surface on which atomic hydrogen and deuterium were co-adsorbed was achieved, following a vibrational mechanism as indicated by the isotope-selectivity. In the present work, selective vibrational IR excitation of adsorbate molecules, treated as multi-dimensional oscillators on dissipative surfaces, has been simulated within the framework of open-system density matrix theory. Not only potential-mediated, inter-mode coupling poses an obstacle to selective excitation but also the coupling of the adsorbate ("system") modes to the electronic and phononic degrees of freedom of the surface ("bath") does. Vibrational relaxation thereby takes place, depending on the availabilty of energetically fitting electron-hole (e/h) pairs and/or phonons (lattice vibrations) in the surface, on time-scales ranging from milliseconds to several hundreds of femtoseconds. On metal surfaces, where the relaxation process of the adsorbate via the e/h pair mechanism dominates, vibrational lifetimes are usually shorter than on insulator or semiconductor surfaces, in the range of picoseconds, being also the timescale of the IR pulses used here. Further inhibiting factors for selectivity can be the harmonicity of a mode and weak dipole activities ("dark modes") rendering vibrational excitation with moderate field intensities difficult. In addition to simple analytical pulses, optimal control theory (OCT) has been employed here to generate a suitable electric field to populate the target state/mode maximally. The complex OCT fields were analyzed by Husimi transformation, resolving the control field in time and energy. The adsorbate/surface systems investigated were CO/Cu(100), H/Si(100) and 2H/Ru(0001). These systems proved to be suitable models to study the above mentioned effects. Further, effects of temperature, pure dephasing (elastic scattering processes), pulse duration and dimensionality (up to four degrees of freedom) were studied. It was possible to selectively excite single vibrational modes, often even state-selective. Special processes like hot-band excitation, vibrationally mediated desorption and the excitation of "dark modes" were simulated. Finally, a novel OCT algorithm in density matrix representation has been developed which allows for time-dependent target operators and thus enables to control the excitation mechanism instead of only the final state. The algorithm is based on a combination of global (iterative) and local (non-iterative) OCT schemes, such that short, globally controlled time-intervals are coupled locally in time. Its numerical performance and accuracy were tested and verified and it was successfully applied to stabilize a two-state linear-combination and to enforce a successive "ladder climbing" in a rather harmonic system, where monochromatic, analytical pulses simultaneously excited several states, leading to a population loss in the target state.
Heterophase polymerization is a technique widely used for the synthesis of high performance polymeric materials with applications including paints, inks, adhesives, synthetic rubber, biomedical applications and many others. Due to the heterogeneous nature of the process, many different relevant length and time scales can be identified. Each of these scales has a direct influence on the kinetics of polymerization and on the physicochemical and performance properties of the final product. Therefore, from the point of view of product and process design and optimization, the understanding of each of these relevant scales and their integration into one single model is a very promising route for reducing the time-to-market in the development of new products, for increasing the productivity and profitability of existing processes, and for designing products with improved performance or cost/performance ratio. The process considered is the synthesis of structured or composite polymer particles by multi-stage seeded emulsion polymerization. This type of process is used for the preparation of high performance materials where a synergistic behavior of two or more different types of polymers is obtained. Some examples include the synthesis of core-shell or multilayered particles for improved impact strength materials and for high resistance coatings and adhesives. The kinetics of the most relevant events taking place in an emulsion polymerization process has been investigated using suitable numerical simulation techniques at their corresponding time and length scales. These methods, which include Molecular Dynamics (MD) simulation, Brownian Dynamics (BD) simulation and kinetic Monte Carlo (kMC) simulation, have been found to be very powerful and highly useful for gaining a deeper insight and achieving a better understanding and a more accurate description of all phenomena involved in emulsion polymerization processes, and can be potentially extended to investigate any type of heterogeneous process. The novel approach of using these kinetic-based numerical simulation methods can be regarded as a complement to the traditional thermodynamic-based macroscopic description of emulsion polymerization. The particular events investigated include molecular diffusion, diffusion-controlled polymerization reactions, particle formation, absorption/desorption of radicals and monomer, and the colloidal aggregation of polymer particles. Using BD simulation it was possible to precisely determine the kinetics of absorption/desorption of molecular species by polymer particles, and to simulate the colloidal aggregation of polymer particles. For diluted systems, a very good agreement between BD simulation and the classical theory developed by Smoluchowski was obtained. However, for concentrated systems, significant deviations from the ideal behavior predicted by Smoluchowski were evidenced. BD simulation was found to be a very valuable tool for the investigation of emulsion polymerization processes especially when the spatial and geometrical complexity of the system cannot be neglected, as is the case of concentrated dispersions, non-spherical particles, structured polymer particles, particles with non-uniform monomer concentration, and so on. In addition, BD simulation was used to describe non-equilibrium monomer swelling kinetics, which is not possible using the traditional thermodynamic approach because it is only valid for systems at equilibrium. The description of diffusion-controlled polymerization reactions was successfully achieved using a new stochastic algorithm for the kMC simulation of imperfectly mixed systems (SSA-IM). In contrast to the traditional stochastic simulation algorithm (SSA) and the deterministic rate of reaction equations, instead of assuming perfect mixing in the whole reactor, the new SSA-IM determines the volume perfectly mixed between two consecutive reactions as a function of the diffusion coefficient of the reacting species. Using this approach it was possible to describe, using a single set of kinetic parameters, typical mass transfer limitations effects during a free radical batch polymerization such as the cage effect, the gel effect and the glass effect. Using multiscale integration it was possible to investigate the formation of secondary particles during the seeded emulsion polymerization of vinyl acetate over a polystyrene seed. Three different cases of radical generation were considered: generation of radicals by thermal decomposition of water-soluble initiating compounds, generation of radicals by a redox reaction at the surface of the particles, and generation of radicals by thermal decomposition of surface-active initiators "inisurfs" attached to the surface of the particles. The simulation results demonstrated the satisfactory reduction in secondary particles formation achieved when the locus of radical generation is controlled close to the particles surface.
In this work the concept of 'context' is considered in five main points. First, context is seen as always necessary for an adequate explication of the concepts of meaning and understanding. Context always plays a role and is not merely brought into consideration when handling a special class of statements or terms, or when there is doubt and clarification is necessary. Second, context cannot be completely reduced to some system of representation. The reason for this is the presence of humans, which is always an important component of a context. Humans experience situations in ways that are not always reducible to symbolic representation. Third, contexts are in principle open. In normal cases they cannot be determined or described in advance. A context is not to be equated with a set of information. Fourth, we understand the parameters of a context pragmatically, which is why we are not led into doubt or even to meaning skepticism by the open nature of a context. This pragmatic knowledge belongs to the category of an ability. Fifth, contexts are, in principle, accessible. This denies the idea that some contexts are incommensurable. There are a number of pragmatic ways of accessing unfamiliar contexts. Some of these are here examined in light of the so-called 'culture wars' in the U.S.A.
Self-Structuring of functionalized micro- and mesoporous organosilicas using boron-silane-precursors
(2008)
The structuring of porous silica materials at the nanometer scale and their surface functionalization are important issues of current materials research. Many innovations in chromatography, catalysis and electronic devices benefit from this knowledge. The work at hand is dedicated to the targeted design of functional organosilica materials. In this context a new precursor concept based on boron-silanes is presented. These precursors combine the properties of a structure directing group and a silica source by covalent borane linkage. Formation of the precursor is easily realized by a sequential two-step hydroboration, firstly on bis(triethoxysilyl)ethene, and secondly on an unsaturated structure directing moiety such as alkenes or polymers. The so prepared precursors self-organize when hydrolysis of their inorganic moiety takes place via an aggregation of their organic side chains into hydrophobic domains. In this way, the additional use of a surfactant as a template is not necessary. Chemical cleavage of these moieties (e.g. by ammonolysis or oxidative saponification) yields an organosilica where all functionalities are exclusively located at the pore wall and therefore accessible. The accessibility of the functionalities is a vital point for applications and is not necessarily granted for common silica functionalization approaches. Further advantages of the boron-silane concept are the possibility to introduce a variety of surface functionalities by heterolytic cleavage of the boron linker and the control of the pore morphology. For that purpose the covalent linkage of different alkyl groups and polymers was studied. Another aspect is the access to chiral boron silane precursors yielding functionalized mesoporous organosilica with chiral functionalities exclusively located at the pore walls after condensation and removal of the structure directing moiety. These materials possess great potential for applications documented by preliminary investigations on chiral resolution of a racemic mixture by HPLC and asymmetric catalysis. In the course of this work valuable insights into the targeted structuring and surface functionalization of organosilicas were gained. A promising outlook for further investigations is the extension of this concept by altering the structure directing moieties of the precursor. That way the morphology of the final organosilica might be controlled by for example mesogens. Furthermore, the use of the boron linker enables the introduction of multiple functionalities into organosilicas, making the obtained material unique in its performance.
Chitooligosaccharides are composed of glycosamin and N-acetylglycisamin residues. Gel permeations chromatography is employed for the separation of oligomers, cation exchange chromatography is used for the separation of homologes and isomers. Trideuterioacetylation of the chitooligosaccharides followed by MALDI-TOF mass spectrometry allowes for the quantitation of mixtures of homologes. vMALDI LTQ multiple-stage MS is employed for quantitative sequencing of complex mixtures of heterochitooligosaccharides. Pure homologes and isomers are applied to biological assays. Chitooligosaccahrides form high-affinity non-covalent complexes with HC gp-39 (human cartilage glycoprotein of 39 kDa). The affinity of the chitooligosaccharides depends on DP, FA and the sequence of glycosamin and N-acetylglycosamin moieties. (+)nanoESI Q TOF MS/MS is used for identification of a high-affinity binding chitooligosaccharide of a non-covalent chitinase B - chitooligosaccharide complex. DADAA is identified as the heterochitoisomer binding with highest affinity and biostability to HC gp-39. Fluorescence based enzyme assays confirm the results.
People engage in a multitude of different relationships. Relatives, spouses, and friends are modestly to moderately similar in various characteristics, e.g., personality characteristics, interests, appearance. The role of psychological (e.g., skills, global appraisal) and social (e.g., gender, familial status) similarities in personal relationships and the association with relationship quality (emotional closeness and reciprocity of support) were examined in four independent studies. Young adults (N = 456; M = 27 years) and middle-aged couples from four different family types (N = 171 couples, M = 38 years) gave answer to a computer-aided questionnaire regarding their ego-centered networks. A subsample of 175 middle-aged adults (77 couples and 21 individuals) participated in a one-year follow-up questioning. Two experimental studies (N = 470; N = 802), both including two assessments with an interval of five weeks, were conducted to examine causal relationships among similarity, closeness, and reciprocity expectations. Results underline the role of psychological and social similarities as covariates of emotional closeness and reciprocity of support on the between-relationship level, but indicate a relatively weak effect within established relationships. In specific relationships, such as parent-child relationships and friendships, psychological similarity partly alleviates the effects of missing genetic relatedness. Individual differences moderate these between-relationship effects. In all, results combine evolutionary and social psychological perspectives on similarity in personal relationships and extend previous findings by means of a network approach and an experimental manipulation of existing relationships. The findings further show that psychological and social similarity have different implications for the study of personal relationships depending on the phase in the developmental process of relationships.
The intention of this master-thesis is a critical assessment of the European Union´s (EU) approach to external democracy promotion in Morocco. The study follows a comparative approach and compares the approach pursued by the EU within the framework of the European Neighbourhood Policy (ENP), incepted in 2004, with the approach that it had developed up until then under the framework of the Euro-Mediterranean Partnership (EMP). The comparison is done with the intention to analyse, to what degree it is justified to speak of a new impetus for democratisation through the ENP in partner countries. The analysis takes into consideration the range of possible instruments for external democracy promotion in the categories „diplomacy“, „conditionality“ and „positive instruments“. For the comparison of democracy promotion under the EMP and the ENP it is suggested to compare the implemented measures in respect to three distinct dimensions: As a first dimension, instruments of democracy promotion are analysed with respect to the focus on indirect vs. direct instruments, e.g. those which aim at establishing socio-economic preconditions favourable to successful democratisation, vs. those which immediately intervene in the processes of political reform. As a second dimension, it is asked whether there has been a shift in the democracy promotion approach on a continuum between consensual cooptation and coercive intervention. As a third dimension, finally, it is analysed whether the approach has undergone a general intensification of efforts, e.g. whether the approach to democracy promotion has become a more active one. The analysis in this master-thesis comes to the conclusion that since the inception of the ENP the EU is indeed pursuing a slightly more direct and certainly a more active approach to democracy promotion in Morocco, while no significant change can be observed in comparison to the strictly partnership-oriented and consensual approach of the EMP. It can be argued that, under the ENP, relations to Morocco have indeed become somewhat more “political”, although at the same time they are still not pro-actively oriented at a political liberalisation of the political regime. Reforms promoted by the EU in Morocco are modest and largely in line with the reform agenda of the Morrocan government itself – e.g. a still largely authoritarian monarchy. Concrete reform steps directed at an opening of the political space, which is largely reserved to the king and its administration, are neither demanded nor supported by democracy promotion instruments, also under the ENP.
Workplace-related anxieties and workplace phobia : a concept of domain-specific mental disorders
(2008)
Background: Anxiety in the workplace is a special problem as workplaces are especially prone to provoke anxiety: There are social hierarchies, rivalries between colleagues, sanctioning through superiors, danger of accidents, failure, and worries of job security. Workplace phobia is a phobic anxiety reaction with symptoms of panic occurring when thinking of or approaching the workplace, and with clear tendency of avoidance. Objectives: What characterizes workplace-related anxieties and workplace phobia as domain-specific mental disorders in contrast to conventional anxiety disorders? Method: 230 patients from an inpatient psychosomatic rehabilitation center were interviewed with the (semi-)structured Mini-Work-Anxiety-Interview and the Mini International Neuropsychiatric Interview, concerning workplace-related anxieties and conventional mental disorders. Additionally, the patients filled in the self-rating questionnaires Job-Anxiety-Scale (JAS) and the Symptom Checklist (SCL-90-R)measuring job-related and general psychosomatic symptom load. Results: Workplace-related anxieties occurred together with conventional anxiety disorders in 35% of the patients, but also alone in others (23%). Workplace phobia could be found in 17% of the interviewed, any diagnosis of workplace-related anxiety was stated in 58%. Workplace phobic patients had significantly higher scores in job-anxiety than patients without workplace phobia. Patients with workplace phobia were significantly longer on sick leave in the past 12 months (23,5 weeks) than patients without workplace phobia (13,4 weeks). Different qualities of workplace-related anxieties lead with different frequencies to work participation disorders. Conclusion: Workplace phobia cannot be described by only assessing the general level of psychosomatic symptom load and conventional mental disorders. Workplace-related anxieties and workplace phobia have an own clinical value which is mainly defined by specific workplace-related symptom load and work-participation disorders. They require special therapeutic attention and treatment instead of a “sick leave” certification by the general health physician. Workplace phobia should be named with a proper diagnosis according to ICD-10 chapter V, F 40.8: “workplace phobia”.
This thesis addresses real-time rendering techniques for 3D information lenses based on the focus & context metaphor. It analyzes, conceives, implements, and reviews its applicability to objects and structures of virtual 3D city models. In contrast to digital terrain models, the application of focus & context visualization to virtual 3D city models is barely researched. However, the purposeful visualization of contextual data of is extreme importance for the interactive exploration and analysis of this field. Programmable hardware enables the implementation of new lens techniques, that allow the augmentation of the perceptive and cognitive quality of the visualization compared to classical perspective projections. A set of 3D information lenses is integrated into a 3D scene-graph system: • Occlusion lenses modify the appearance of virtual 3D city model objects to resolve their occlusion and consequently facilitate the navigation. • Best-view lenses display city model objects in a priority-based manner and mediate their meta information. Thus, they support exploration and navigation of virtual 3D city models. • Color and deformation lenses modify the appearance and geometry of 3D city models to facilitate their perception. The presented techniques for 3D information lenses and their application to virtual 3D city models clarify their potential for interactive visualization and form a base for further development.
This thesis provides a novel view on the early stage of crystallization utilizing calcium carbonate as a model system. Calcium carbonate is of great economical, scientific and ecological importance, because it is a major part of water hardness, the most abundant Biomineral and forms huge amounts of geological sediments thus binding large amounts of carbon dioxide. The primary experiments base on the evolution of supersaturation via slow addition of dilute calcium chloride solution into dilute carbonate buffer. The time-dependent measurement of the Ca2+ potential and concurrent pH = constant titration facilitate the calculation of the amount of calcium and carbonate ions bound in pre-nucleation stage clusters, which have never been detected experimentally so far, and in the new phase after nucleation, respectively. Analytical Ultracentrifugation independently proves the existence of pre-nucleation stage clusters, and shows that the clusters forming at pH = 9.00 have a proximately time-averaged size of altogether 70 calcium and carbonate ions. Both experiments show that pre-nucleation stage cluster formation can be described by means of equilibrium thermodynamics. Effectively, the cluster formation equilibrium is physico-chemically characterized by means of a multiple-binding equilibrium of calcium ions to a ‘lattice’ of carbonate ions. The evaluation gives GIBBS standard energy for the formation of calcium/carbonate ion pairs in clusters, which exhibits a maximal value of approximately 17.2 kJ mol^-1 at pH = 9.75 and relates to a minimal binding strength in clusters at this pH-value. Nucleated calcium carbonate particles are amorphous at first and subsequently become crystalline. At high binding strength in clusters, only calcite (the thermodynamically stable polymorph) is finally obtained, while with decreasing binding strength in clusters, vaterite (the thermodynamically least stable polymorph) and presumably aragonite (the thermodynamically intermediate stable polymorph) are obtained additionally. Concurrently, two different solubility products of nucleated amorphous calcium carbonate (ACC) are detected at low binding strength and high binding strength in clusters (ACC I 3.1EE-8 M^2, ACC II 3.8EE-8 M^2), respectively, indicating the precipitation of at least two different ACC species, while the clusters provide the precursor species of ACC. It is proximate that ACC I may relate to calcitic ACC –i.e. ACC exhibiting short range order similar to the long range order of calcite and that ACC II may relate to vateritic ACC, which will subsequently transform into the particular crystalline polymorph as discussed in the literature, respectively. Detailed analysis of nucleated particles forming at minimal binding strength in clusters (pH = 9.75) by means of SEM, TEM, WAXS and light microscopy shows that predominantly vaterite with traces of calcite forms. The crystalline particles of early stages are composed of nano-crystallites of approximately 5 to 10 nm size, respectively, which are aligned in high mutual order as in mesocrystals. The analyses of precipitation at pH = 9.75 in presence of additives –polyacrylic acid (pAA) as a model compound for scale inhibitors and peptides exhibiting calcium carbonate binding affinity as model compounds for crystal modifiers- shows that ACC I and ACC II are precipitated in parallel: pAA stabilizes ACC II particles against crystallization leading to their dissolution for the benefit of crystals that form from ACC I and exclusively calcite is finally obtained. Concurrently, the peptide additives analogously inhibit the formation of calcite and exclusively vaterite is finally obtained in case of one of the peptide additives. These findings show that classical nucleation theory is hardly applicable for the nucleation of calcium carbonate. The metastable system is stabilized remarkably due to cluster formation, while clusters forming by means of equilibrium thermodynamics are the nucleation relevant species and not ions. Most likely, the concept of cluster formation is a common phenomenon occurring during the precipitation of hardly soluble compounds as qualitatively shown for calcium oxalate and calcium phosphate. This finding is important for the fundamental understanding of crystallization and nucleation-inhibition and modification by additives with impact on materials of huge scientific and industrial importance as well as for better understanding of the mass transport in crystallization. It can provide a novel basis for simulation and modelling approaches. New mechanisms of scale formation in Bio- and Geomineralization and also in scale inhibition on the basis of the newly reported reaction channel need to be considered.
Nanostructured inorganic materials are routinely synthesized by the use of templates. Depending on the synthesis conditions of the product material, either “soft” or “hard” templates can be applied. For sol-gel processes, usually “soft” templating techniques are employed, while “hard” templates are used for high temperature synthesis pathways. In classical templating approaches, the template has the unique role of structure directing agent, in the sense that it is not participating to the chemical formation of the resulting material. This work investigates a new templating pathway to nanostructured materials, where the template is also a reagent in the formation of the final material. This concept is described as “reactive templating” and opens a synthetic path toward materials which cannot be synthesised on a nanometre scale by classical templating approaches. Metal nitrides are such kind of materials. They are usually produced by the conversion of metals or metal oxides in ammonia flow at high temperature (T > 1000°C), which make the application of classical templating techniques difficult. Graphitic carbon nitride, g-C3N4, despite its fundamental and theoretical importance, is probably one of the most promising materials to complement carbon in material science and many efforts are put in the synthesis of this material. A simple polyaddition/elimination reaction path at high temperature (T = 550°C) allows the polymerisation of cyanamide toward graphitic carbon nitride solids. By hard templating, using nanostructured silica or aluminium oxide as nanotemplates, a variety of nanostructured graphitic carbon nitrides such as nanorods, nanotubes, meso- and macroporous powders could be obtained by nanocasting or nanocoating. Due to the special semi-conducting properties of the graphitic carbon nitride matrix, the nanostructured graphitic carbon nitrides show unexpected catalytic activity for the activation of benzene in Friedel-Crafts type reactions, making this material an interesting metal free catalyst. Furthermore, due to the chemical composition of g-C3N4 and the fact that it is totally decomposed at temperatures between 600°C and 800°C even under inert atmosphere, g-C3N4 was shown to be a good nitrogen donor for the synthesis of early transition metal nitrides at high temperatures. Thus using the nanostructured carbon nitrides as “reactive templates” or “nanoreactors”, various metal nitride nanostructures, such as nanoparticles and porous frameworks could be obtained at high temperature. In this approach the carbon nitride nanostructure played both the role of the nitrogen source and of the exotemplate, imprinting its size and shape to the resulting metal nitride nanostructure.
For the first time stabilizer-free vinylidene fluoride (VDF) polymerizations were carried out in homogeneous phase with supercritical CO₂. Polymerizations were carried out at 140°C, 1500 bar and were initiated with di-tert-butyl peroxide (DTBP). In-line FT-NIR (Fourier Transform- Near Infrared) spectroscopy showed that complete monomer conversion may be obtained. Molecular weights were determined via size-exclusion chromatography (SEC) and polymer end group analysis by 1H-NMR spectroscopy. The number average molecular weights were below 104 g∙mol−1 and polydispersities ranged from 3.1 to 5.7 depending on DTBP and VDF concentration. To allow for isothermal reactions high CO₂ contents ranging from 61 to 83 wt.% were used. The high-temperature, high-pressure conditions were required for homogeneous phase polymerization. These conditions did not alter the amount of defects in VDF chaining. Scanning electron microscopy (SEM) indicated that regular stack-type particles were obtained upon expansion of the homogeneous polymerization mixture. To reduce the required amount of initiator, further VDF polymerizations using chain transfer agents (CTAs) to control molecular weights were carried out in homogeneous phase with supercritical carbon dioxide (scCO₂) at 120 °C and 1500 bar. Using perfluorinated hexyl iodide as CTA, polymers of low polydispersity ranging from 1.5 to 1.2 at the highest iodide concentration of 0.25 mol·L-1 were obtained. Electrospray ionization- mass spectroscopy (ESI-MS) indicates the absence of initiator derived end groups, supporting livingness of the system. The “livingness” is based on the labile C-I bond. However, due to the weakness of the C-I bond perfluorinated hexyl iodide also contributes to initiation. To allow for kinetic analyses of VDF polymerizations the CTA should not contribute to initiation. Therefore, additional CTAs were applied: BrCCl3, C6F13Br and C6F13H. It was found that C6F13H does not contribute to initiation. At 120°C and 1500 bar kp/kt0.5~ 0.64 (L·mol−1·s−1)0.5 was derived. The chain transfer constant (CT) at 120°C has been determined to be 8·10−1, 9·10−2 and 2·10−4 for C6F13I, C6F13Br and C6F13H, respectively. These CT values are associated with the bond energy of the C-X bond. Moreover, the labile C-I bond allows for functionalization of the polymer to triazole end groups applying click reactions. After substitution of the iodide end group by an azide group 1,3 dipolar cycloadditions with alkynes yield polymers with 1,2,3 triazole end groups. Using symmetrical alkynes the reactions may be carried out in the absence of any catalyst. This end-functionalized poly (vinylidene fluoride) (PVDF) has higher thermal stability as compared to the normal PVDF. PVDF samples from homogeneous phase polymerizations in supercritical CO₂ and subsequent expansion to ambient conditions were analyzed with respect to polymer end groups, crystallinity, type of polymorphs and morphology. Upon expansion the polymer was obtained as white powder. Scanning electron microscopy (SEM) showed that DTBP derived polymer end groups led to stack-type particles whereas sponge- or rose-type particles were obtained in case of CTA fragments as end groups. Fourier-Transform Infrared spectroscopy and wide angle X-ray diffraction indicated that the type of polymorph, α or β crystal phase was significantly affected by the type of end group. The content of β-phase material, which is responsible for piezoelectricity of PVDF, is the highest for polymer with DTBP-derived end groups. In addition, the crystallinity of the material, as determined via differential scanning calorimetry is affected by the end groups and polymer molecular weights. For example, crystallinity ranges from around 26 % for DTBP-derived end groups to a maximum of 62 % for end groups originating from perfluorinated hexyl iodide for polymers with Mn ~2200 g·mol–1. Expansion of the homogeneous polymerization mixture results in particle formation by a non-optimized RESS (Rapid Expansion from Supercritical Solution) process. Thus, it was tested how polymer end groups affect the particles size distribution obtained from RESS process under controlled conditions (T = 50°C and P = 200 bar). In all RESS experiments, small primary PVDF with diameters less than 100 nm without the use of liquid solvents, surfactants, or other additives were produced. A strong correlation between particle size and particle size distribution with polymer end groups and molecular weight of the original material was observed. The smallest particles were found for RESS of PVDF with Mn~ 4000 g·mol–1 and PFHI (C6F13I) - derived end groups.
Landscapes evolve in a complex interplay between climate and tectonics. Thus, the geomorphic characteristics of a landscape can only be understood if both, climatic and tectonic signals of past and ongoing processes can be identified. In order to evaluate the impact of both forcing factors it is crucial to quantify the evolution of geomorphic markers in natural environments. The Cenozoic Andes are an ideal setting to evaluate tectonic and climatic aspects of landscape evolution at different time and length scales in different natural compartments. The Andean Cordillera constitutes the type subduction orogen and is associated with the subduction of the oceanic Nazca Plate beneath the South American continent since at least 200 million years. In Chile and the adjacent regions this convergent margin is characterized by active tectonics, volcanism, and mountain building. Importantly, along the coast of Chile megathrust earthquakes occur frequently and influence landscape evolution. In fact, the largest earthquake ever recorded occurred in south-central Chile in 1960 and comprised a rupture zone of ~ 1000 km length. However, on longer time scales beyond historic documentation of seismicity it is not well known, how such seismotectonic segments have behaved and how they influence the geomorphic evolution of the coastal realms. With several semi-independent morphotectonic segments, recurrent megathrust earthquakes, and a plethora of geomorphic features indicating sustained tectonism, the margin of Chile is thus a key area to study relationships between surface processes and tectonics. In this study, I combined geomorphology, geochronology, sedimentology, and morphometry to quantify the Pliocene-Pleistocene landscape evolution of the tectonically active south-central Chile forearc. Thereby, I provide (1) new results about the influence of seismotectonic forearc segmentation on the geomorphic evolution and (2) new insights in the interaction between climate and tectonics with respect to the morphology of the Chilean forearc region. In particular, I show that the forearc is characterized by three long-term segments that are not correlated with short-lived earthquake-rupture zones that may. These segments are the Nahuelbuta, Toltén, and Bueno segments, each recording a distinct geomorphic and tectonic evolution. The Nahuelbuta and Bueno segments are undergoing active tectonic uplift. The long-term behavior of these two segments is manifested in form of two doubly plunging, growing antiforms that constitute an integral part of the Coastal Cordillera and record the uplift of marine and river terraces. In addition, these uplifting areas have caused major changes in flow directions or rivers. In contrast, the Toltén segment, situated between the two other segments, appears to be quasi-stable. In order to further quantify uplift and incision in the actively deforming Nahuelbuta segment, I dated an erosion surface and fluvial terraces in the Coastal Cordillera with cosmogenic 10Be and 26Al and optically stimulated luminescence, respectively. According to my results, late Pleistocene uplift rates corresponding to 0.88 mm a-1 are faster than surface-uplift rates averaging over the last 5 Ma, which are in the range of 0.21 mm a-1. This discrepancy suggests that surface uplift is highly variable in time and space and might preferably concentrate along reverse faults as indicated by a late Pleistocene flow reversal. In addition, the results of exposure dating with cosmogenic 10Be and 26Al indicate that the morphotectonic segmentation of this region of the forearc has been established in Pliocene time, coeval with the initiation of uplift of the Coastal Cordillera about 5 Ma ago, inferred to be related to a shift in subduction mode from erosion to accretion. Finally, I dated volcanic clasts obtained from alluvial surfaces in the Central Depression, a low-relief sector separating the Coastal from the Main Cordillera, with stable cosmogenic 3He and 21Ne, in order to reveal the controls of sediment accumulation in the forearc. My results document that these gently sloping surfaces have been deposited 150 to 300 ka ago. This deposition may be related to changes in the erosional regime during glacial episodes. Taken together, the data indicates that the overall geomorphic expression of the forearc is of post-Miocene age and may be intimately related to a climatic overprint of the tectonic system. This climatic forcing is also reflected in the topography and local relief of the Central and Southern Andes that vary considerably along the margin, determined by the dominant surface process that in turn is eventually controlled by climate. However, relief also partly reflects surface processes that have taken place under past climatic conditions. This emphasizes that due care has to be exercised when interpreting landscapes as mirrors of modern climates.
This paper compares police reforms during democratization in Poland, Hungary, and Bosnia-Herzegovina. It analyses the changes to the structure of the democratic control of the police in each reform, paying special attention to the decentralization versus centralization aspect of it. The research question of this paper is: Why are some states decentralizing the democratic control of the police, while others are centralizing it, both with the aim of democratization? The theoretical background of this study are theories about policy diffusion and policy transfer. Therefore this study can be categorized as part of two different research areas. On the one hand, it is a paper from the discipline of International Relations. On the other hand, it is a paper from the discipline of Comparative Politics. The combined attention to international and national factors influencing police reform is reflected by the structure of this paper. Chapter 3 examines police structures and police reforms in established democracies as possible role models for new democracies. Chapter 4 looks at international and transnational actors that actively try to influence police reform. After having examined these external factors, three cases of police reform in new democracies are examined in chapter 5.