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Hybrid nanomaterials offer the combination of individual properties of different types of nanoparticles. Some strategies for the development of new nanostructures in larger scale rely on the self-assembly of nanoparticles as a bottom-up approach. The use of templates provides ordered assemblies in defined patterns. In a typical soft-template, nanoparticles and other surface-active agents are incorporated into non-miscible liquids. The resulting self-organized dispersions will mediate nanoparticle interactions to control the subsequent self-assembly. Especially interactions between nanoparticles of very different dispersibility and functionality can be directed at a liquid-liquid interface.
In this project, water-in-oil microemulsions were formulated from quasi-ternary mixtures with Aerosol-OT as surfactant. Oleyl-capped superparamagnetic iron oxide and/or silver nanoparticles were incorporated in the continuous organic phase, while polyethyleneimine-stabilized gold nanoparticles were confined in the dispersed water droplets. Each type of nanoparticle can modulate the surfactant film and the inter-droplet interactions in diverse ways, and their combination causes synergistic effects. Interfacial assemblies of nanoparticles resulted after phase-separation. On one hand, from a biphasic Winsor type II system at low surfactant concentration, drop-casting of the upper phase afforded thin films of ordered nanoparticles in filament-like networks. Detailed characterization proved that this templated assembly over a surface is based on the controlled clustering of nanoparticles and the elongation of the microemulsion droplets. This process offers versatility to use different nanoparticle compositions by keeping the surface functionalization, in different solvents and over different surfaces. On the other hand, a magnetic heterocoagulate was formed at higher surfactant concentration, whose phase-transfer from oleic acid to water was possible with another auxiliary surfactant in ethanol-water mixture. When the original components were initially mixed under heating, defined oil-in-water, magnetic-responsive nanostructures were obtained, consisting on water-dispersible nanoparticle domains embedded by a matrix-shell of oil-dispersible nanoparticles.
Herein, two different approaches were demonstrated to form diverse hybrid nanostructures from reverse microemulsions as self-organized dispersions of the same components. This shows that microemulsions are versatile soft-templates not only for the synthesis of nanoparticles, but also for their self-assembly, which suggest new approaches towards the production of new sophisticated nanomaterials in larger scale.
In my doctoral thesis, I examine continuous gravity measurements for monitoring of the geothermal site at Þeistareykir in North Iceland. With the help of high-precision superconducting gravity meters (iGravs), I investigate underground mass changes that are caused by operation of the geothermal power plant (i.e. by extraction of hot water and reinjection of cold water). The overall goal of this research project is to make a statement about the sustainable use of the geothermal reservoir, from which also the Icelandic energy supplier and power plant operator Landsvirkjun should benefit.
As a first step, for investigating the performance and measurement stability of the gravity meters, in summer 2017, I performed comparative measurements at the gravimetric observatory J9 in Strasbourg. From the three-month gravity time series, I examined calibration, noise and drift behaviour of the iGravs in comparison to stable long-term time series of the observatory superconducting gravity meters. After preparatory work in Iceland (setup of gravity stations, additional measuring equipment and infrastructure, discussions with Landsvirkjun and meetings with the Icelandic partner institute ISOR), gravity monitoring at Þeistareykir was started in December 2017. With the help of the iGrav records of the initial 18 months after start of measurements, I carried out the same investigations (on calibration, noise and drift behaviour) as in J9 to understand how the transport of the superconducting gravity meters to Iceland may influence instrumental parameters.
In the further course of this work, I focus on modelling and reduction of local gravity contributions at Þeistareykir. These comprise additional mass changes due to rain, snowfall and vertical surface displacements that superimpose onto the geothermal signal of the gravity measurements. For this purpose, I used data sets from additional monitoring sensors that are installed at each gravity station and adapted scripts for hydro-gravitational modelling. The third part of my thesis targets geothermal signals in the gravity measurements.
Together with my PhD colleague Nolwenn Portier from France, I carried out additional gravity measurements with a Scintrex CG5 gravity meter at 26 measuring points within the geothermal field in the summers of 2017, 2018 and 2019. These annual time-lapse gravity measurements are intended to increase the spatial coverage of gravity data from the three continuous monitoring stations to the entire geothermal field. The combination of CG5 and iGrav observations, as well as annual reference measurements with an FG5 absolute gravity meter represent the hybrid gravimetric monitoring method for Þeistareykir. Comparison of the gravimetric data to local borehole measurements (of groundwater levels, geothermal extraction and injection rates) is used to relate the observed gravity changes to the actually extracted (and reinjected) geothermal fluids. An approach to explain the observed gravity signals by means of forward modelling of the geothermal production rate is presented at the end of the third (hybrid gravimetric) study. Further modelling with the help of the processed gravity data is planned by Landsvirkjun. In addition, the experience from time-lapse and continuous gravity monitoring will be used for future gravity measurements at the Krafla geothermal field 22 km south-east of Þeistareykir.
Cardiac valves are essential for the continuous and unidirectional flow of blood throughout the body. During embryonic development, their formation is strictly connected to the mechanical forces exerted by blood flow. The endocardium that lines the interior of the heart is a specialized endothelial tissue and is highly sensitive to fluid shear stress. Endocardial cells harbor a signal transduction machinery required for the translation of these forces into biochemical signaling, which strongly impacts cardiac morphogenesis and physiology. To date, we lack a solid understanding on the mechanisms by which endocardial cells sense the dynamic mechanical stimuli and how they trigger different cellular responses. In the zebrafish embryo, endocardial cells at the atrioventricular canal respond to blood flow by rearranging from a monolayer to a double-layer, composed of a luminal cell population subjected to blood flow and an abluminal one that is not exposed to it. These early morphological changes lead to the formation of an immature valve leaflet. While previous studies mainly focused on genes that are positively regulated by shear stress, the mechanisms regulating cell behaviors and fates in cells that lack the stimulus of blood flow are largely unknown. One key discovery of my work is that the flow-sensitive Notch receptor and Krüppel-like factor (Klf) 2, one of the best characterized flow-regulated transcriptional factors, are activated by shear stress but that they function in two parallel signal transduction pathways. Each of these two pathways is essential for the rearrangement of atrioventricular cells into an immature double-layered valve leaflets. A second key discovery of my study is the finding that both Notch and Klf2 signaling negatively regulate the expression of the angiogenesis receptor Vegfr3/Flt4, which becomes restricted to abluminal endocardial cells of the valve leaflet. Within these cells, Flt4 downregulates the expressions of the cell adhesion proteins Alcam and VE-cadherin. A loss of Flt4 causes abluminal endocardial cells to ectopically express Notch, which is normally restricted to luminal cells, and impairs valve morphology. My study suggests that abluminal endocardial cells that do not experience mechanical stimuli loose Notch expression and this triggers expression of Flt4. In turn, Flt4 negatively regulates Notch on the abluminal side of the valve leaflet. These antagonistic signaling activities and fine-tuned gene regulatory mechanisms ultimately shape cardiac valve leaflets by inducing unique differences in the fates of endocardial cells.
This project describes the nominal, verbal and ‘truncation’ systems of Awing and explains the syntactic and semantic functions of the multifunctional l<-><-> (LE) morpheme in copular and wh-focused constructions. Awing is a Bantu Grassfields language spoken in the North West region of Cameroon. The work begins with morphological processes viz. deverbals, compounding, reduplication, borrowing and a thorough presentation of the pronominal system and takes on verbal categories viz. tense, aspect, mood, verbal extensions, negation, adverbs and triggers of a homorganic N(asal)-prefix that attaches to the verb and other verbal categories. Awing grammar also has a very unusual phenomenon whereby nouns and verbs take long and short forms. A chapter entitled truncation is dedicated to the phenomenon. It is observed that the truncation process does not apply to bare singular NPs, proper names and nouns derived via morphological processes. On the other hand, with the exception of the 1st person non-emphatic possessive determiner and the class 7 noun prefix, nouns generally take the truncated form with modifiers (i.e., articles, demonstratives and other possessives). It is concluded that nominal truncation depicts movement within the DP system (Abney 1987). Truncation of the verb occurs in three contexts: a mass/plurality conspiracy (or lattice structuring in terms of Link 1983) between the verb and its internal argument (i.e., direct object); a means to align (exhaustive) focus (in terms of Fery’s 2013), and a means to form polar questions.
The second part of the work focuses on the role of the LE morpheme in copular and wh-focused clauses. Firstly, the syntax of the Awing copular clause is presented and it is shown that copular clauses in Awing have ‘subject-focus’ vs ‘topic-focus’ partitions and that the LE morpheme indirectly relates such functions. Semantically, it is shown that LE does not express contrast or exhaustivity in copular clauses. Turning to wh-constructions, the work adheres to Hamblin’s (1973) idea that the meaning of a question is the set of its possible answers and based on Rooth’s (1985) underspecified semantic notion of alternative focus, concludes that the LE morpheme is not a Focus Marker (FM) in Awing: LE does not generate or indicate the presence of alternatives (Krifka 2007); The LE morpheme can associate with wh-elements as a focus-sensitive operator with semantic import that operates on the focus alternatives by presupposing an exhaustive answer, among other notions. With focalized categories, the project further substantiates the claim in Fominyam & Šimík (2017), namely that exhaustivity is part of the semantics of the LE morpheme and not derived via contextual implicature, via a number of diagnostics. Hence, unlike in copular clauses, the LE morpheme with wh-focused categories is analysed as a morphological exponent of a functional head Exh corresponding to Horvath's (2010) EI (Exhaustive Identification). The work ends with the syntax of verb focus and negation and modifies the idea in Fominyam & Šimík (2017), namely that the focalized verb that associates with the exhaustive (LE) particle is a lower copy of the finite verb that has been moved to Agr. It is argued that the LE-focused verb ‘cluster’ is an instantiation of adjunction. The conclusion is that verb doubling with verb focus in Awing is neither a realization of two copies of one and the same verb (Fominyam and Šimík 2017), nor a result of a copy triggered by a focus marker (Aboh and Dyakonova 2009). Rather, the focalized copy is said to be merged directly as the complement of LE forming a type of adjoining cluster.
Understanding how organisms adapt to their local environment is a major focus of evolutionary biology. Local adaptation occurs when the forces of divergent natural selection are strong enough compared to the action of other evolutionary forces. An improved understanding of the genetic basis of local adaptation can inform about the evolutionary processes in populations and is of major importance because of its relevance to altered selection pressures due to climate change. So far, most insights have been gained by studying model organisms, but our understanding about the genetic basis of local adaptation in wild populations of species with little genomic resources is still limited.
With the work presented in this thesis I therefore set out to provide insights into the genetic basis of local adaptation in populations of two voles species: the common vole (Microtus arvalis) and the bank vole (Myodes glareolus). Both voles species are small mammals, they have a high evolutionary potential compared to their dispersal capabilities and are thus likely to show genetic responses to local conditions, moreover, they have a wide distribution in which they experience a broad range of different environmental conditions, this makes them an ideal species to study local adaptation.
The first study focused on producing a novel mitochondrial genome to facilitate further research in M. arvalis. To this end, I generated the first mitochondrial genome of M. arvalis using shotgun sequencing and an iterative mapping approach. This was subsequently used in a phylogenetic analysis that produced novel insights into the phylogenetic relationships of the Arvicolinae.
The following two studies then focused on the genetic basis of local adaptation using ddRAD-sequencing data and genome scan methods. The first of these involved sequencing the genomic DNA of individuals from three low-altitude and three high-altitude M. arvalis study sites in the Swiss Alps. High-altitude environments with their low temperatures and low levels of oxygen (hypoxia) pose considerable challenges for small mammals. With their small body size and proportional large body surface they have to sustain high rates of aerobic metabolism to support thermogenesis and locomotion, which can be restricted with only limited levels of oxygen available. To generate insights into high-altitude adaptation I identified a large number of single nucleotide polymorphisms (SNPs). These data were first used to identify high levels of differentiation between study sites and a clear pattern of population structure, in line with a signal of isolation by distance. Using genome scan methods, I then identified signals of selection associated with differences in altitude in genes with functions related to oxygen transport into tissue and genes related to aerobic metabolic pathways. This indicates that hypoxia is an important selection pressure driving local adaptation at high altitude in M. arvalis. A number of these genes were linked with high-altitude adaptation in other species before, which lead to the suggestion that high-altitude populations of several species have evolved in a similar manner as a response to the unique conditions at high altitude
The next study also involved the genetic basis of local adaptation, here I provided insights into climate-related adaptation in M. glareolus across its European distribution. Climate is an important environmental factor affecting the physiology of all organisms. In this study I identified a large number of SNPs in individuals from twelve M. glareolus populations distributed across Europe. I used these, to first establish that populations are highly differentiated and found a strong pattern of population structure with signal of isolation by distance. I then employed genome scan methods to identify candidate loci showing signals of selection associated with climate, with a particular emphasis on polygenic loci. A multivariate analysis was used to determine that temperature was the most important climate variable responsible for adaptive genetic variation among all variables tested. By using novel methods and genome annotation of related species I identified the function of genes of candidate loci. This showed that genes under selection have functions related to energy homeostasis and immune processes. Suggesting that M. glareolus populations have evolved in response to local temperature and specific local pathogenic selection pressures.
The studies presented in this thesis provide evidence for the genetic basis of local adaptation in two vole species across different environmental gradients, suggesting that the identified genes are involved in local adaptation. This demonstrates that with the help of novel methods the study of wild populations, which often have little genomic resources available, can provide unique insights into evolutionary processes.
Stimuli-promoted in situ formation of hydrogels with thiol/thioester containing peptide precursors
(2022)
Hydrogels are potential synthetic ECM-like substitutes since they provide functional and structural similarities compared to soft tissues. They can be prepared by crosslinking of macromolecules or by polymerizing suitable precursors. The crosslinks are not necessarily covalent bonds, but could also be formed by physical interactions such as π-π interactions, hydrophobic interactions, or H-bonding. On demand in situ forming hydrogels have garnered increased interest especially for biomedical applications over preformed gels due to the relative ease of in vivo delivery and filling of cavities. The thiol-Michael addition reaction provides a straightforward and robust strategy for in situ gel formation with its fast reaction kinetics and ability to proceed under physiological conditions. The incorporation of a trigger function into a crosslinking system becomes even more interesting since gelling can be controlled with stimulus of choice. The use of small molar mass crosslinker precursors with active groups orthogonal to thiol-Michael reaction type electrophile provides the opportunity to implement an on-demand in situ crosslinking without compromising the fast reaction kinetics.
It was postulated that short peptide sequences due to the broad range structural-function relations available with the different constituent amino acids, can be exploited for the realisation of stimuli-promoted in situ covalent crosslinking and gelation applications. The advantages of this system over conventional polymer-polymer hydrogel systems are the ability tune and predict material property at the molecular level.
The main aim of this work was to develop a simplified and biologically-friendly stimuli-promoted in situ crosslinking and hydrogelation system using peptide mimetics as latent crosslinkers. The approach aims at using a single thiodepsipeptide sequence to achieve separate pH- and enzyme-promoted gelation systems with little modification to the thiodepsipeptide sequence. The realization of this aim required the completion of three milestones.
In the first place, after deciding on the thiol-Michael reaction as an effective in situ crosslinking strategy, a thiodepsipeptide, Ac-Pro-Leu-Gly-SLeu-Leu-Gly-NEtSH (TDP) with expected propensity towards pH-dependent thiol-thioester exchange (TTE) activation, was proposed as a suitable crosslinker precursor for pH-promoted gelation system. Prior to the synthesis of the proposed peptide-mimetic, knowledge of the thiol-Michael reactivity of the would-be activated thiol moiety SH-Leu, which is internally embedded in the thiodepsipeptide was required. In line with pKa requirements for a successful TTE, the reactivity of a more acidic thiol, SH-Phe was also investigated to aid the selection of the best thiol to be incorporated in the thioester bearing peptide based crosslinker precursor. Using ‘pseudo’ 2D-NMR investigations, it was found that only reactions involving SH-Leu yielded the expected thiol-Michael product, an observation that was attributed to the steric hindrance of the bulkier nature of SH-Phe. The fast reaction rates and complete acrylate/maleimide conversion obtained with SH-Leu at pH 7.2 and higher aided the direct elimination of SH-Phe as a potential thiol for the synthesis of the peptide mimetic.
Based on the initial studies, for the pH-promoted gelation system, the proposed Ac-Pro-Leu-Gly-SLeu-Leu-Gly-NEtSH was kept unmodified. The subtle difference in pKa values between SH-Leu (thioester thiol) and the terminal cysteamine thiol from theoretical conditions should be enough to effect a ‘pseudo’ intramolecular TTE. In polar protic solvents and under basic aqueous conditions, TDP successfully undergoes a ‘pseudo’ intramolecular TTE reaction to yield an α,ω-dithiol tripeptide, HSLeu-Leu-Gly-NEtSH. The pH dependence of thiolate ion generation by the cysteamine thiol aided the incorporation of the needed stimulus (pH) for the overall success of TTE (activation step) – thiol-Michael addition (crosslinking) strategy.
Secondly, with potential biomedical applications in focus, the susceptibility of TDP, like other thioesters, to intermolecular TTE reaction was probed with a group of thiols of varying thiol pKa values, since biological milieu characteristically contain peptide/protein thiols. L-cysteine, which is a biologically relevant thiol, and a small molecular weight thiol, methylthioglycolate both with relatively similar thiol pKa, values, led to an increase concentration of the dithiol crosslinker when reacted with TDP. In the presence of acidic thiols (p-NTP and 4MBA), a decrease in the dithiol concentration was observed, an observation that can be attributed to the inability of the TTE tetrahedral intermediate to dissociate into exchange products and is in line with pKa requirements for successful TTE reaction. These results additionally makes TDP more attractive and the potentially the first crosslinker precursor for applications in biologically relevant media.
Finally, the ability of TDP to promote pH-sensitive in situ gel formation was probed with maleimide functionalized 4-arm polyethylene glycol polymers in tris-buffered media of varying pHs. When a 1:1 thiol: maleimide molar ratio was used, TDP-PEG4MAL hydrogels formed within 3, 12 and 24 hours at pH values of 8.5, 8.0 and 7.5 respectively. However, gelation times of 3, 5 and 30 mins were observed for the same pH trend when the thiol: maleimide molar was increased to 2:1.
A direct correlation of thiol content with G’ of the gels at each pH could also be drawn by comparing gels with thiol: maleimide ratios of 1:1 to those with 2:1 thiol: maleimide mole ratios. This is supported by the fact that the storage modulus (G') is linearly dependent on the crosslinking density of the polymer. The values of initial G′ for all gels ranged between (200 – 5000 Pa), which falls in the range of elasticities of certain tissue microenvironments for example brain tissue 200 – 1000 Pa and adipose tissue (2500 – 3500 Pa).
Knowledge so far gained from the study on the ability to design and tune the exchange reaction of thioester containing peptide mimetic will give those working in the field further insight into the development of new sequences tailored towards specific applications.
TTE substrate design using peptide mimetic as presented in this work has revealed interesting new insights considering the state-of-the-art. Using the results obtained as reference, the strategy provides a possibility to extend the concept to the controlled delivery of active molecules needed for other robust and high yielding crosslinking reactions for biomedical applications. Application for this sequentially coupled functional system could be seen e.g. in the treatment of inflamed tissues associated with urinary tract like bladder infections for which pH levels above 7 were reported. By the inclusion of cell adhesion peptide motifs, the hydrogel network formed at this pH could act as a new support layer for the healing of damage epithelium as shown in interfacial gel formation experiments using TDP and PEG4MAL droplets.
The versatility of the thiodepsipeptide sequence, Ac-Pro-Leu-Gly-SLeu-Leu-Gly-(TDPo) was extended for the design and synthesis of a MMP-sensitive 4-arm PEG-TDPo conjugate. The purported cleavage of TDPo at the Gly-SLeu bond yields active thiol units for subsequent reaction of orthogonal Michael acceptor moieties. One of the advantages of stimuli-promoted in situ crosslinking systems using short peptides should be the ease of design of required peptide molecules due to the predictability of peptide functions their sequence structure. Consequently the functionalisation of a 4-arm PEG core with the collagenase active TDPo sequence yielded an MMP-sensitive 4-arm thiodepsipeptide-PEG conjugate (PEG4TDPo) substrate.
Cleavage studies using thiol flourometric assay in the presence of MMPs -2 and -9 confirmed the susceptibility of PEG4TDPo towards these enzymes. The resulting time-dependent increase in fluorescence intensity in the presence of thiol assay signifies the successful cleavage of TDPo at the Gly-SLeu bond as expected. It was observed that the cleavage studies with thiol flourometric assay introduces a sigmoid non-Michaelis-Menten type kinetic profile, hence making it difficult to accurately determine the enzyme cycling parameters, kcat and KM .
Gelation studies with PEG4MAL at 10 % wt. concentrations revealed faster gelation with MMP-2 than MMP-9 with 28 and 40 min gelation times respectively. Possible contributions by hydrolytic cleavage of PEG4TDPo has resulted in the gelation of PEG4MAL blank samples but only after 60 minutes of reaction. From theoretical considerations, the simultaneous gelation reaction would be expected to more negatively impact the enzymatic than hydrolytic cleavage. The exact contributions from hydrolytic cleavage of PEG4TDPo would however require additional studies.
In summary this new and simplified in situ crosslinking system using peptide-based crosslinker precursors with tuneable properties exhibited in situ crosslinking gelation kinetics on similar levels with already active dithiols reported. The advantageous on-demand functionality associated with its pH-sensitivity and physiological compatibility makes it a strong candidate worth further research as biomedical applications in general and on-demand material synthesis is concerned.
Results from MMP-promoted gelation system unveils a simple but unexplored approach for in situ synthesis of covalently crosslinked soft materials, that could lead to the development of an alternative pathway in addressing cancer metastasis by making use of MMP overexpression as a trigger. This goal has so far not being reach with MMP inhibitors despite the extensive work this regard.
Modern biological analysis techniques supply scientists with various forms of data. One category of such data are the so called "expression data". These data indicate the quantities of biochemical compounds present in tissue samples. Recently, expression data can be generated at a high speed. This leads in turn to amounts of data no longer analysable by classical statistical techniques. Systems biology is the new field that focuses on the modelling of this information. At present, various methods are used for this purpose. One superordinate class of these methods is machine learning. Methods of this kind had, until recently, predominantly been used for classification and prediction tasks. This neglected a powerful secondary benefit: the ability to induce interpretable models. Obtaining such models from data has become a key issue within Systems biology. Numerous approaches have been proposed and intensively discussed. This thesis focuses on the examination and exploitation of one basic technique: decision trees. The concept of comparing sets of decision trees is developed. This method offers the possibility of identifying significant thresholds in continuous or discrete valued attributes through their corresponding set of decision trees. Finding significant thresholds in attributes is a means of identifying states in living organisms. Knowing about states is an invaluable clue to the understanding of dynamic processes in organisms. Applied to metabolite concentration data, the proposed method was able to identify states which were not found with conventional techniques for threshold extraction. A second approach exploits the structure of sets of decision trees for the discovery of combinatorial dependencies between attributes. Previous work on this issue has focused either on expensive computational methods or the interpretation of single decision trees a very limited exploitation of the data. This has led to incomplete or unstable results. That is why a new method is developed that uses sets of decision trees to overcome these limitations. Both the introduced methods are available as software tools. They can be applied consecutively or separately. That way they make up a package of analytical tools that usefully supplement existing methods. By means of these tools, the newly introduced methods were able to confirm existing knowledge and to suggest interesting and new relationships between metabolites.
Die Publikation zu Sprachwandelprozessen im Russischen und Ukrainischen beschreibt eine ausschlaggebende Phase der neueren Sprachgeschichte Russlands und der Ukraine (1985–2008). Im Fokus steht die Anglisierung als eine der Haupttendenzen der aktuellen sprachlichen Destandardisierung europäischer Sprachen. Die Autorin zeigt am Beispiel der Anglisierung in der Werbesprache die Destandardisierung des Russischen und Ukrainischen nach 1985 auf. Diese korpusbasierte Untersuchung umfasst sowohl die quantitative (statistische) als auch die qualitative (systemlinguistische) Analyse des werbesprachlichen Korpus. Die quantitative chronologische Analyse belegt die deutlich stärkere Dynamik der Anglisierung im Ukrainischen nach 1998. Die qualitative Analyse illustriert die unterschiedlichen bzw. gemeinsamen innerlinguistischen Prozesse in beiden Sprachen, insbesondere Anglizismen-Integration und Standardisierungswege.
Besteuerung von Unternehmensgewinnen im Licht des Konzepts der konsumorientierten Einkommensteuer
(2011)
Die Dissertation widmet sich dem Problem der fiskalischen Konsequenzen der konsumorientierten Steuern, die die unternehmerischen Gewinne unabhängig von der Rechtsform belasten. Im empirischen Teil der Arbeit wird der Untersuchungsgegenstand auf die zinsbereinigte Gewinnsteuer (allowance for corporate equity) eingegrenzt. Die Untersuchung beruht auf theoretischen Überlegungen sowie einer eigenen Simulationsanalyse. Den Schwerpunkt bilden dabei zwei Kategorien, zwischen denen ein kausaler Zusammenhang vorliegt: die Gestaltung der Bemessungsgrundlage einerseits und die Erfüllung der Fiskalfunktion andererseits. Das Hauptziel der Arbeit ist es, die fiskalischen Konsequenzen einer nach dem Konzept der Konsumorientierung modifizierten Bemessungsgrundlage der Gewinnsteuern zu überprüfen. Die Abschätzung der fiskalischen Konsequenzen wird aufgrund der vier folgenden Bereiche vorgenommen: (1) theoretische Konzepte der konsumorientierten Einkommensteuer, (2) bisherige Umsetzungen der Konzepte der konsumorientierten Gewinnsteuer, (3) bisherige Untersuchungen der konsumorientierten Gewinnsteuer, (4) eine eigene Simulation der fiskalischen Konsequenzen der konsumorientierten Gewinnsteuer. Um das Hauptziel der Arbeit zu erreichen, werden acht in Form von Teilfragen ausformulierte Untersuchungsprobleme gelöst. Sie betreffen sowohl die theoretischen Ausführungen, als auch die empirische Untersuchung. Dabei entsprechen sie den einzelnen Untersuchungsschritten, die in den aufeinander folgenden Kapiteln der Arbeit durchgeführt werden. Anhand der Analyse der bisherigen wissenschaftlichen Erkenntnisse und der praktischen Umsetzungen des Konzepts der konsumorientierten Steuern wurde die folgende Haupthypothese aufgestellt: Der Ausfall des Steueraufkommens, der ein direkter Effekt der Gestaltung der Bemessungsgrundlage nach dem Konzept der Konsumorientierung ist, schließt die Fiskalfunktion der Gewinnsteuern nicht aus. Das Verfahren, das eine Verifizierung der Haupthypothese zum Ziel hat, erfolgt durch eine Untersuchung von drei Teilhypothesen: der Hypothese über die Nullsteuer, der Hypothese über den differenzierten Aufkommensausfall und der Hypothese über die Konzentration der Steuerschuld. In der Dissertation werden empirische Daten aus drei Quellen benutzt. Sie umfassen einen Teil der in Polen in den Jahren 2004-2008 tätigen Unternehmen und ermöglichen es, eine Simulationsanalyse des Aufkommensausfalls durchzuführen. Diese bedient sich der Methodik der Mikro- und Gruppensimulation, was in den bisherigen Untersuchungen zur Unternehmensbesteuerung ein eher selten anzutreffender Ansatz ist. Die gewonnenen Ergebnisse zeigen, dass die Steuereinnahmen aus der Einkommensteuer und der Körperschaftsteuer durch die Modifizierung der Bemessungsgrundlage deutlich reduziert werden. Die relativ große fiskalische Bedeutung der beiden Steuern bleibt jedoch erhalten und der Ausfall des Steueraufkommens, der direkt nach der Einführung einer konsumorientierten Steuerreform eintreten würde, wäre der „Preis“ für eine bessere, weniger verzerrende Bemessungsgrundlage. Die Dissertation liefert Ergebnisse, die für die Gestaltung der Steuerpolitik in Polen wie auch in anderen Ländern relevant sind. Dies scheint insbesondere im Kontext des häufig diskutierten Umbaus des Systems der Einkommen- und Gewinnbesteuerung bedeutsam. Darüber hinaus bildet die Arbeit einen Ausgangspunkt für weitere, vertiefte Untersuchungen zu den möglichen Gestaltungsformen der Einkommen- und Gewinnsteuern wie auch zu deren Folgen. Die Methode der Steuersimulation kann weiterentwickelt werden und in anderen Analysen der potenziellen Konsequenzen von Steuerreformen Anwendung finden.
A key non-destructive technique for analysis, optimization and developing of new functional materials such as sensors, transducers, electro-optical and memory devices is presented. The Thermal-Pulse Tomography (TPT) provides high-resolution three-dimensional images of electric field and polarization distribution in a material. This thermal technique use a pulsed heating by means of focused laser light which is absorbed by opaque electrodes. The diffusion of the heat causes changes in the sample geometry, generating a short-circuit current or change in surface potential, which contains information about the spatial distribution of electric dipoles or space charges. Afterwards, a reconstruction of the internal electric field and polarization distribution in the material is possible via Scale Transformation or Regularization methods. In this way, the TPT was used for the first time to image the inhomogeneous ferroelectric switching in polymer ferroelectric films (candidates to memory devices). The results shows the typical pinning of electric dipoles in the ferroelectric polymer under study and support the previous hypotheses of a ferroelectric reversal at a grain level via nucleation and growth. In order to obtain more information about the impact of the lateral and depth resolution of the thermal techniques, the TPT and its counterpart called Focused Laser Intensity Modulation Method (FLIMM) were implemented in ferroelectric films with grid-shaped electrodes. The results from both techniques, after the data analysis with different regularization and scale methods, are in total agreement. It was also revealed a possible overestimated lateral resolution of the FLIMM and highlights the TPT method as the most efficient and reliable thermal technique. After an improvement in the optics, the Thermal-Pulse Tomography method was implemented in polymer-dispersed liquid crystals (PDLCs) films, which are used in electro-optical applications. The results indicated a possible electrostatic interaction between the COH group in the liquid crystals and the fluorinate atoms of the used ferroelectric matrix. The geometrical parameters of the LC droplets were partially reproduced as they were compared with Scanning Electron Microscopy (SEM) images. For further applications, it is suggested the use of a non-strong-ferroelectric polymer matrix. In an effort to develop new polymerferroelectrets and for optimizing their properties, new multilayer systems were inspected. The results of the TPT method showed the non-uniformity of the internal electric-field distribution in the shaped-macrodipoles and thus suggested the instability of the sample. Further investigation on multilayers ferroelectrets was suggested and the implementation of less conductive polymers layers too.
Starch is a biopolymer for which, despite its simple composition, understanding the precise mechanism behind its formation and regulation has been challenging. Several approaches and bioanalytical tools can be used to expand the knowledge on the different parts involved in the starch metabolism. In this sense, a comprehensive analysis targeting two of the main groups of molecules involved in this process: proteins, as effectors/regulators of the starch metabolism, and maltodextrins as starch components and degradation products, was conducted in this research work using potato plants (Solanum tuberosum L. cv. Desiree) as model of study. On one side, proteins physically interacting to potato starch were isolated and analyzed through mass spectrometry and western blot for their identification. Alternatively, starch interacting proteins were explored in potato tubers from transgenic plants having antisense inhibition of starch-related enzymes and on tubers stored under variable environmental conditions. Most of the proteins recovered from the starch granules corresponded to previously described proteins having a specific role in the starch metabolic pathway. Another set of proteins could be grouped as protease inhibitors, which were found weakly interacting to starch. Variations in the protein profile obtained after electrophoresis separation became clear when tubers were stored under different temperatures, indicating a differential expression of proteins in response to changing environmental conditions.
On the other side, since maltodextrin metabolism is thought to be involved in both starch initiation and degradation, soluble maltooligosaccharide content in potato tubers was analyzed in this work under diverse experimental variables. For this, tuber disc samples from wild type and transgenic lines strongly repressing either the plastidial or cytosolic form of the -glucan phosphorylase and phosphoglucomutase were incubated with glucose, glucose-6-phosphate, and glucose-1-phosphate solutions to evaluate the influence of such enzymes on the conversion of the carbon sources into soluble maltodextrins, in comparison to wild-type samples. Relative maltodextrin amounts analyzed through capillary electrophoresis equipped with laser-induced fluorescence (CE-LIF) revealed that tuber discs could immediately uptake glucose-1-phosphate and use it to produce maltooligosaccharides with a degree of polymerization of up to 30 (DP30), in contrast to transgenic tubers with strong repression of the plastidial glucan phosphorylase. The results obtained from the maltodextrin analysis support previous indications that a specific transporter for glucose-1-phosphate may exist in both the plant cells and the plastidial membranes, thereby allowing a glucose-6-phosphate independent transport. Furthermore, it confirms that the plastidial glucan phosphorylase is responsible for producing longer maltooligosaccharides in the plastids by catalyzing a glucan polymerization reaction when glucose-1-phosphate is available. All these findings contribute to a better understanding of the role of the plastidial glucan phosphorylase as a key enzyme directly involved in the synthesis and degradation of glucans and their implication on starch metabolism.
Obwohl der sozioökonomische Status (SES) eine in der Sozialepidemiologie häufig gebrauchte Variable darstellt, ist seine Verwendung mit methodischen Problemen verknüpft: Seine latente Struktur führt dazu, dass sich verschiedene Möglichkeiten der Operationalisierung eröffnen. Diese reichen von klassischen Ungleichheitsindikatoren wie Bildung, Einkommen oder Berufsposition, über multidimensionale oder über Nachbarschaftsmerkmale konstruierte Indizes, bis hin zu subjektiven Statuseinschätzungen. Problematisch ist dies insofern, als verschiedene Indikatoren auf unterschiedlichen theoretischen Konstrukten beruhen und unterschiedliche Schlussfolgerungen erlauben.
In dieser Arbeit wird deshalb in einem ersten Schritt anhand eines systematischen Reviews zum Zusammenhang von SES und Rückenschmerzen überprüft, welche Indikatoren in wissenschaftlichen Publikationen eingesetzt werden und wie die Auswahl begründet wird. Das Ergebnis zeigt eine klare Präferenz für klassische Indikatoren (Bildung, Einkommen und Berufsposition). Erläutert wurde die jeweilige Auswahl allerdings nur in einem geringen Prozentsatz der untersuchten Artikel, obwohl die unterschiedlichen Studienergebnisse nahelegen, dass der gewählte Indikator einen Einfluss auf den gefundenen Zusammenhang ausüben könnte.
Deshalb wurde in einem weiteren Schritt überprüft, wie unterschiedliche SES-Indikatoren mit der Verbesserung von Rückenschmerzen nach einer Rehabilitation (Studie 1) und der Neuentstehung von Rückenschmerzen (Studie 2) zusammenhängen. Außerdem wurde untersucht, ob ein einfaches Modell den Zusammenhang von SES und Gesundheit so darstellen kann, dass a priori abzuschätzen ist, wie hoch der Einfluss unterschiedlicher Indikatoren auf einen bestimmten Gesundheitsoutput sein könnte.
Es zeigt sich, dass sich der errechnete Zusammenhang zwischen den verschiedenen Indikatoren und chronischen Rückenschmerzen erheblich unterscheidet: Für Menschen, die bereits wegen Rückenschmerzen in Rehabilitation waren, erwiesen sich Bildung und Berufsposition als ähnlich einflussreiche Einflussfaktoren, während für das Einkommen kein bedeutender Zusammenhang festgestellt werden konnte. Für die Neuentstehung chronischer Rückenschmerzen zeigte sich die Berufsposition als wichtigster Indikator, gefolgt von Bildung, während für Einkommen kein signifikanter Zusammenhang gefunden werden konnte.
Folglich bestimmt die Wahl des Indikators die Höhe des festgestellten Zusammenhangs stark mit. Unterschiedliche Indikatoren dürfen deshalb nicht als austauschbar betrachtet werden und es muss bei jeder Forschungsfrage genau überlegt werden, welcher Indikator für die jeweilige Fragestellung am besten verwendet werden kann. Das vorgeschlagene theoretische Modell kann dabei als Unterstützung dienen.
Im Rahmen des ersten Teils der vorliegenden Doktorarbeit konnten zwei nicht-essentielle (rps15, rpl36) und fünf essentielle (rps3, rps16, rpl22, rpl23, rpl32) im Plastom von Nicotiana tabacum kodierte Proteine des plastidären Ribosoms bezüglich ihrer Essentialität charakterisiert werden. Diese Gene wurden durch gezielte Knockout-Experimente inaktiviert und die resultierenden Effekte untersucht. Die Ergebnisse lassen einen Rückschluss auf die Lokalisation der Gene der insgesamt sieben untersuchten ribosomalen Proteine zu, die im Plastom mehrerer parasitischer, Plastiden-besitzender Spezies nicht mehr nachweisbar sind. Im Fall von rps15 könnte tatsächlich ein Verlust des Genes stattgefunden haben, im Fall der restlichen Gene ist eher mit einem Transfer in den Nukleus zu rechnen (rpl36 ausgenommen). Dies würde bedeuten, dass die Geschwindigkeit der erfolgreichen Etablierung eines Gentransfers in vielen parasitischen Spezies gegenüber grünen Pflanzen stark erhöht ist. Alle in E. coli nicht-essentiellen Proteine mit Homologen in Plastiden (rps15, rpl33, rpl36) sind auch dort, trotz ~1,5 Milliarden Jahren getrennter Evolution, nicht essentiell. Dieses Ergebnis bestätigt den schon früher festgestellten hohen Konservierungsgrad der bakteriellen und plastidären Translationsmaschinerien. Die Phänotypen der KO-Pflanzen der nicht-essentiellen Gene (rps15, rpl36) weisen auf eine interessante Rolle von S15 während der Ribosomenassemblierung hin und im Fall von L36 auf eine wichtige funktionelle Rolle im Plastiden-Ribosomen sowie auf eine Involvierung der Plastidentranslation in der Generierung eines retrograden Signals, welches die Blattform zu beeinflussen im Stande ist. Des Weiteren konnte eine Verbindung der Translationsaktivität mit der Ausbildung von Seitentrieben hergestellt werden, die vermutlich auf veränderte Auxinsynthese im Chloroplast zurückzuführen ist. Aus dem Folgeprojekt, bei dem Doppel-KO-Pflanzen nicht-essentieller ribosomaler Proteine erzeugt wurden, lässt sich auf eine relativ große Plastizität der Architektur von Plastidenribosomen schließen. Im zweiten Teil der Arbeit konnte erfolgreich ein Hochdurchsatz-Screeningsystem zur semiquantitativen Analyse von 192 verschiedenen miRNAs aus Chlamydomonas reinhardtii etabliert werden. Es gelang durch die Untersuchung von 23 verschiedenen Wachstums- und Stressbedingungen sowie Entwicklungsstadien mehrere miRNAs zu identifizieren, die eine differenzielle Expression zeigen sowie unter allen untersuchten Bedingungen konstant bleibende miRNAs nachzuweisen. Dadurch konnten mehrere vielversprechende Kandidaten-miRNAs ausgemacht werden, die nun eingehender untersucht werden können.
Neuronale Verarbeitung emotionaler Prosodie und Syntax : die Rolle des verbalen Arbeitsgedächnisses
(2008)
An important strand of research has investigated the question of how children acquire a morphological system using offline data from spontaneous or elicited child language. Most of these studies have found dissociations in how children apply regular and irregular inflection (Marcus et al. 1992, Weyerts & Clahsen 1994, Rothweiler & Clahsen 1993). These studies have considerably deepened our understanding of how linguistic knowledge is acquired and organised in the human mind. Their methodological procedures, however, do not involve measurements of how children process morphologically complex forms in real time. To date, little is known about how children process inflected word forms. The aim of this study is to investigate children’s processing of inflected words in a series of on-line reaction time experiments. We used a cross-modal priming experiment to test for decompositional effects on the central level. We used a speeded production task and a lexical decision task to test for frequency effects on access level in production and recognition. Children’s behaviour was compared to adults’ behaviour towards three participle types (-t participles, e.g. getanzt ‘danced’ vs. -n participles with stem change, e.g. gebrochen ‘broken’ vs.-n participles without stem change, e.g. geschlafen ‘slept’). For the central level, results indicate that -t participles but not -n participles have decomposed representations. For the access level, results indicate that -t participles are represented according to their morphemes and additionally as full forms, at least from the age of nine years onwards (Pinker 1999 and Clahsen et al. 2004). Further evidence suggested that -n participles are represented as full-form entries on access level and that -n participles without stem change may encode morphological structure (cf. Clahsen et al. 2003). Out data also suggests that processing strategies for -t participles are differently applied in recognition and production. These results provide evidence that children (within the age range tested) employ the same mechanisms for processing participles as adults. The child lexicon grows as children form additional full-form representations for -t participles on access level and elaborate their full-form lexical representations of -n participles on central level. These results are consistent with processing as explained in dual-system theories.
This study follows the debate in comparative public administration research on the role of advisory arrangements in central governments. The aim of this study is to explain the mechanisms by which these actors gain their alleged role in government decision-making. Hence, it analyses advisory arrangements that are proactively involved in executive decision-making and may compete with the permanent bureaucracy by offering policy advice to political executives. The study argues that these advisory arrangements influence government policy-making by "institutional politics", i.e. by shaping the institutional underpinnings to govern or rather the "rules of the executive game" in order to strengthen their own position or that of their clients. The theoretical argument of this study follows the neo-institutionalist turn in organization theory and defines institutional politics as gradual institutionalization processes between institutions and organizational actors. It applies a broader definition of institutions as sets of regulative, normative and cognitive pillars. Following the "power-distributional approach" such gradual institutionalization processes are influenced by structure-oriented characteristics, i.e. the nature of the objects of institutional politics, in particular the freedom of interpretation in their application, as well as the distinct constraints of the institutional context. In addition, institutional politics are influenced by agency-oriented characteristics, i.e. the ambitions of actors to act as "would-be change agents". These two explanatory dimensions result in four ideal-typical mechanisms of institutional politics: layering, displacement, drift, and conversion, which correspond to four ideal-types of would-be change agents. The study examines the ambitions of advisory arrangements in institutional politics in an exploratory manner, the relevance of the institutional context is analyzed via expectation hypotheses on the effects of four institutional context features that are regarded as relevant in the scholarly debate: (1) the party composition of governments, (2) the structuring principles in cabinet, (3) the administrative tradition, and (4) the formal politicization of the ministerial bureaucracy. The study follows a "most similar systems design" and conducts qualitative case studies on the role of advisory arrangements at the center of German and British governments, i.e. the Prime Minister’s Office and the Ministry of Finance, for a longer period (1969/1970-2005). Three time periods are scrutinized per country; the British case studies examine the role of advisory arrangements at the Cabinet Office, the Prime Minister's Office, and the Ministry of Finance under Prime Ministers Heath (1970-74), Thatcher (1979-87) and Blair (1997-2005). The German case studies study the role of advisory arrangements at the Federal Chancellery and the Federal Ministry of Finance during the Brandt government (1969-74), the Kohl government (1982-1987) and the Schröder government (1998-2005). For the empirical analysis, the results of a document analysis and the findings of 75 semi-structured expert interviews have been triangulated. The comparative analysis reveals different patterns of institutional politics. The German advisory arrangements engaged initially in displacement but turned soon towards layering and drift, i.e. after an initial displacement of the pre-existing institutional underpinnings to govern they laid increasingly new elements onto existing ones and took the non-deliberative decision to neglect the adaption of existing rules of the executive game towards changing environmental demands. The British advisory arrangements were mostly involved in displacement and conversion, despite occasional layering, i.e. they displaced the pre-existing institutional underpinnings to govern with new rules of the executive game and transformed and realigned them, sometimes also layering new elements onto pre-existing ones. The structure- and agency-oriented characteristics explain these patterns of institutional politics. First, the study shows that the institutional context limits the institutional politics in Germany and facilitates the institutional politics in the UK. Second, the freedom of interpreting the application of institutional targets is relevant and could be observed via the different ambitions of advisory arrangements across countries and over time, confirming, third, that the interests of such would-be change agents are likewise important to understand the patterns of institutional politics. The study concludes that the role of advisory arrangements in government policy-making rests not only upon their policy-related, party-political or media-advisory role for political executives, but especially upon their activities in institutional politics, resulting in distinct institutional constraints on all actors in government policy-making – including their own role in these processes.
Design and development of novel three color-FRET systems in synthetic peptides and oligonucleotides
(2012)
As climate change worsens, there is a growing urgency to promote renewable energies and improve their accessibility to society. Here, solar energy harvesting is of particular importance. Currently, metal halide perovskite (MHP) solar cells are indispensable in future solar energy generation research. MHPs are crystalline semiconductors increasingly relevant as low-cost, high-performance materials for optoelectronics. Their processing from solution at low temperature enables easy fabrication of thin film elements, encompassing solar cells and light-emitting diodes or photodetectors. Understanding the coordination chemistry of MHPs in their precursor solution would allow control over the thin film crystallization, the material properties and the final device performance.
In this work, we elaborate on the key parameters to manipulate the precursor solution with the long-term objective of enabling systematic process control. We focus on the nanostructural characterization of the initial arrangements of MHPs in the precursor solutions. Small-angle scattering is particularly well suited for measuring nanoparticles in solution. This technique proved to be valuable for the direct analyzes of perovskite precursor solutions in standard processing concentrations without causing radiation damage. We gain insights into the chemical nature of widely used precursor structures such as methylammonium lead iodide (MAPbI3), presenting first insights into the complex arrangements and interaction within this precursor state. Furthermore, we transfer the preceding results to other more complex perovskite precursors. The influence of compositional engineering is investigated using the addition of alkali cations as an example. As a result, we propose a detailed working mechanism on how the alkali cations suppress the formation of intermediate phases and improve the quality of the crystalline thin film. In addition, we investigate the crystallization process of a tin-based perovskite composition (FASnI3) under the influence of fluoride chemistry. We prove that the frequently used additive, tin fluoride (SnF2), selectively binds undesired oxidized tin (Sn(IV)) in the precursor solution. This prevents its incorporation into the actual crystal structure and thus reduces the defect density of the material. Furthermore, SnF2 leads to a more homogeneous crystal growth process, which results in improved crystal quality of the thin film material.
In total, this study provides a detailed characterization of the complex system of perovskite precursor chemistry. We thereby cover relevant parameters for future MHP solar cell process control, such as (I) the environmental impact based on concentration and temperature (II) the addition of counter ions to reduce the diffuse layer surrounding the precursor nanostructures and (III) the targeted use of additives to eliminate unwanted components selectively and to ensure a more homogeneous crystal growth.
With the many challenges facing the agricultural system, such as water scarcity, loss of arable land due to climate change, population growth, urbanization or trade disruptions, new agri-food systems are needed to ensure food security in the future. In addition, healthy diets are needed to combat non-communicable diseases. Therefore, plant-based diets rich in health-promoting plant secondary metabolites are desirable. A saline indoor farming system is representing a sustainable and resilient new agrifood system and can preserve valuable fresh water. Since indoor farming relies on artificial lighting, assessment of lighting conditions is essential. In this thesis, the cultivation of halophytes in a saline indoor farming system was evaluated and the influence of cultivation conditions were assessed in favor of improving the nutritional quality of halophytes for human consumption. Therefore, five selected edible halophyte species (Brassica oleracea var. palmifolia, Cochlearia officinalis, Atriplex hortensis, Chenopodium quinoa, and Salicornia europaea) were cultivated in saline indoor farming. The halophyte species were selected for to their salt tolerance levels and mechanisms. First, the suitability of halophytes for saline indoor farming and the influence of salinity on their nutritional properties, e.g. plant secondary metabolites and minerals, were investigated. Changes in plant performance and nutritional properties were observed as a function of salinity. The response to salinity was found to be species-specific and related to the salt tolerance mechanism of the halophytes. At their optimal salinity levels, the halophytes showed improved carotenoid content. In addition, a negative correlation was found between the nitrate and chloride content of halophytes as a function of salinity. Since chloride and nitrate can be antinutrient compounds, depending on their content, monitoring is essential, especially in halophytes. Second, regional brine water was introduced as an alternative saline water resource in the saline indoor farming system. Brine water was shown to be feasible for saline indoor farming
of halophytes, as there was no adverse effect on growth or nutritional properties, e.g. carotenoids. Carotenoids were shown to be less affected by salt composition than by salt concentration. In addition, the interaction between the salinity and the light regime in indoor farming and greenhouse cultivation has been studied. There it was shown that interacting light regime and salinity alters the content of carotenoids and chlorophylls. Further, glucosinolate and nitrate content were also shown to be influenced by light regime. Finally, the influence of UVB light on halophytes was investigated using supplemental narrow-band UVB LEDs. It was shown that UVB light affects the growth, phenotype and metabolite profile of halophytes and that the UVB response is species specific. Furthermore, a modulation of carotenoid content in S. europaea could be achieved to enhance health-promoting properties and thus improve nutritional quality. This was shown to be dose-dependent and the underlying mechanisms of carotenoid accumulation were also investigated. Here it was revealed that carotenoid accumulation is related to oxidative stress.
In conclusion, this work demonstrated the potential of halophytes as alternative vegetables produced in a saline indoor farming system for future diets that could contribute to ensuring food security in the future. To improve the sustainability of the saline indoor farming system, LED lamps and regional brine water could be integrated into the system. Since the nutritional properties have been shown to be influenced by salt, light regime and UVB light, these abiotic stressors must be taken into account when considering halophytes as alternative vegetables for human nutrition.
Die Beeinflussung optischer Eigenschaften durch Bestrahlung stellt eine Grundlage für die Herstellung anisotroper optischer Komponenten dar. In dünnen Schichten von Azobenzen-Polymeren kann optische Anisotropie durch linear polarisierte Bestrahlung induziert oder modifiziert werden. Ziel der Arbeit war es, wesentliche Struktur-Eigenschafts-Beziehungen zum Prozess der Photoorientierung zu erarbeiten, um so eine Optimierung der Materialien für verschiedene Anwendungen ermöglichen. In isotropen Schichten flüssigkristalliner und amorpher Azobenzen-Polymeren wird das Ausmaß der induzierten optischen Anisotropie günstig durch eine Donor/Akzeptor-Substitution in 4,4'-Position beeinflusst. Die Induktionsgeschwindigkeit ist in Schichten flüssigkristalliner Polymeren deutlich geringer, jedoch lassen sich höhere Werte der Doppelbrechung und des Dichroismus erreichen. In Copolymeren bewirkt die Photoorientierung der Azobenzen-Seitengruppen eine kooperative Orientierung von formanisotropen Seitengruppen. Die Mesogenität der nicht-photochromen Seitengruppen erhöht das Ausmaß der induzierten optischen Anisotropie. Die Stabilität der induzierten Doppelbrechung und des Dichroismus wird durch diese Gruppen gesteigert. In Schichten flüssigkristalliner Polymeren wird die induzierte optische Anisotropie beim Tempern im Bereich der Mesophasen erheblich verstärkt. Dabei reicht ein geringes Maß an induzierter Anisotropie aus, um Doppelbrechungs- und Dichroismuswerte zu erzielen, wie sie für LC-Domänen typisch sind. In orientierten Schichten von Azobenzen-Polymeren wird das Resultat der linear polarisierten Bestrahlung durch die Stärke der anisotropen Wechselwirkungen in den flüssigkristallinen Domänen oder den LB-Multilayern bestimmt. Eine lichtinduzierte Reorientierung kann nur erreicht werden, wenn diese Wechselwirkungen überwunden werden können. Erfolgt eine Photoreorientierung in den orientierten Polymerschichten, werden in Copolymeren formanisotrope Seitengruppen ebenfalls kooperativ reorientiert. Eine vorgelagerte UV-Bestrahlung kann durch Erzeugung eines hohen Anteils an nicht-mesogenen Z-Isomeren die anisotropen Wechselwirkungen stark schwächen und so die Seitengruppen entkoppeln. Aus diesem Zustand erfolgt die Photoreorientierung mit einer der Photoorientierung in isotropen Schichten vergleichbaren Effizienz. Die erarbeiteten Struktur-Eigenschafts-Beziehungen liefern einen Beitrag zur Optimierung derartiger Materialien für Anwendungen in den Bereichen optischer Funktionsschichten, holographischer Datenspeicherung oder der Generierung von Oberflächenreliefgittern.
High-mountain regions provide valuable ecosystem services, including food, water, and energy production, to more than 900 million people worldwide. Projections hold, that this population number will rapidly increase in the next decades, accompanied by a continued urbanisation of cities located in mountain valleys. One of the manifestations of this ongoing socio-economic change of mountain societies is a rise in settlement areas and transportation infrastructure while an increased power need fuels the construction of hydropower plants along rivers in the high-mountain regions of the world. However, physical processes governing the cryosphere of these regions are highly sensitive to changes in climate and a global warming will likely alter the conditions in the headwaters of high-mountain rivers. One of the potential implications of this change is an increase in frequency and magnitude of outburst floods – highly dynamic flows capable of carrying large amounts of water and sediments. Sudden outbursts from lakes formed behind natural dams are complex geomorphological processes and are often part of a hazard cascade. In contrast to other types of natural hazards in high-alpine areas, for example landslides or avalanches, outburst floods are highly infrequent. Therefore, observations and data describing for example the mode of outburst or the hydraulic properties of the downstream propagating flow are very limited, which is a major challenge in contemporary (glacial) lake outburst flood research. Although glacial lake outburst floods (GLOFs) and landslide-dammed lake outburst floods (LLOFs) are rare, a number of documented events caused high fatality counts and damage. The highest documented losses due to outburst floods since the start of the 20th century were induced by only a few high-discharge events. Thus, outburst floods can be a significant hazard to downvalley communities and infrastructure in high-mountain regions worldwide.
This thesis focuses on the Greater Himalayan region, a vast mountain belt stretching across 0.89 million km2. Although potentially hundreds of outburst floods have occurred there since the beginning of the 20th century, data on these events is still scarce. Projections of cryospheric change, including glacier-mass wastage and permafrost degradation, will likely result in an overall increase of the water volume stored in meltwater lakes as well as the destabilisation of mountain slopes in the Greater Himalayan region. Thus, the potential for outburst floods to affect the increasingly more densely populated valleys of this mountain belt is also likely to increase in the future. A prime example of one of these valleys is the Pokhara valley in Nepal, which is drained by the Seti Khola, a river crossing one of the steepest topographic gradients in the Himalayas. This valley is also home to Nepal’s second largest, rapidly growing city, Pokhara, which currently has a population of more than half a million people – some of which live in informal settlements within the floodplain of the Seti Khola. Although there is ample evidence for past outburst floods along this river in recent and historic times, these events have hardly been quantified.
The main motivation of my thesis is to address the data scarcity on past and potential future outburst floods in the Greater Himalayan region, both at a regional and at a local scale. For the former, I compiled an inventory of >3,000 moraine-dammed lakes, of which about 1% had a documented sudden failure in the past four decades. I used this data to test whether a number of predictors that have been widely applied in previous GLOF assessments are statistically relevant when estimating past GLOF susceptibility. For this, I set up four Bayesian multi-level logistic regression models, in which I explored the credibility of the predictors lake area, lake-area dynamics, lake elevation, parent-glacier-mass balance, and monsoonality. By using a hierarchical approach consisting of two levels, this probabilistic framework also allowed for spatial variability on GLOF susceptibility across the vast study area, which until now had not been considered in studies of this scale. The model results suggest that in the Nyainqentanglha and Eastern Himalayas – regions with strong negative glacier-mass balances – lakes have been more prone to release GLOFs than in regions with less negative or even stable glacier-mass balances. Similarly, larger lakes in larger catchments had, on average, a higher probability to have had a GLOF in the past four decades. Yet, monsoonality, lake elevation, and lake-area dynamics were more ambiguous. This challenges the credibility of a lake’s rapid growth in surface area as an indicator of a pending outburst; a metric that has been applied to regional GLOF assessments worldwide.
At a local scale, my thesis aims to overcome data scarcity concerning the flow characteristics of the catastrophic May 2012 flood along the Seti Khola, which caused 72 fatalities, as well as potentially much larger predecessors, which deposited >1 km³ of sediment in the Pokhara valley between the 12th and 14th century CE. To reconstruct peak discharges, flow depths, and flow velocities of the 2012 flood, I mapped the extents of flood sediments from RapidEye satellite imagery and used these as a proxy for inundation limits. To constrain the latter for the Mediaeval events, I utilised outcrops of slackwater deposits in the fills of tributary valleys. Using steady-state hydrodynamic modelling for a wide range of plausible scenarios, from meteorological (1,000 m³ s-1) to cataclysmic outburst floods (600,000 m³ s-1), I assessed the likely initial discharges of the recent and the Mediaeval floods based on the lowest mismatch between sedimentary evidence and simulated flood limits. One-dimensional HEC-RAS simulations suggest, that the 2012 flood most likely had a peak discharge of 3,700 m³ s-1 in the upper Seti Khola and attenuated to 500 m³ s-1 when arriving in Pokhara’s suburbs some 15 km downstream.
Simulations of flow in two-dimensions with orders of magnitude higher peak discharges in ANUGA show extensive backwater effects in the main tributary valleys. These backwater effects match the locations of slackwater deposits and, hence, attest for the flood character of Mediaeval sediment pulses. This thesis provides first quantitative proof for the hypothesis, that the latter were linked to earthquake-triggered outbursts of large former lakes in the headwaters of the Seti Khola – producing floods with peak discharges of >50,000 m³ s-1.
Building on this improved understanding of past floods along the Seti Khola, my thesis continues with an analysis of the impacts of potential future outburst floods on land cover, including built-up areas and infrastructure mapped from high-resolution satellite and OpenStreetMap data. HEC-RAS simulations of ten flood scenarios, with peak discharges ranging from 1,000 to 10,000 m³ s-1, show that the relative inundation hazard is highest in Pokhara’s north-western suburbs. There, the potential effects of hydraulic ponding upstream of narrow gorges might locally sustain higher flow depths. Yet, along this reach, informal settlements and gravel mining activities are close to the active channel. By tracing the construction dynamics in two of these potentially affected informal settlements on multi-temporal RapidEye, PlanetScope, and Google Earth imagery, I found that exposure increased locally between three- to twentyfold in just over a decade (2008 to 2021).
In conclusion, this thesis provides new quantitative insights into the past controls on the susceptibility of glacial lakes to sudden outburst at a regional scale and the flow dynamics of propagating flood waves released by past events at a local scale, which can aid future hazard assessments on transient scales in the Greater Himalayan region. My subsequent exploration of the impacts of potential future outburst floods to exposed infrastructure and (informal) settlements might provide valuable inputs to anticipatory assessments of multiple risks in the Pokhara valley.
Konrad und Gurkenkönig jenseits der Pyrenäen : Christine Nöstlinger auf Spanisch und Katalanisch
(2005)
In dieser Arbeit werden nichtlineare Kopplungsmechanismen von akustischen Oszillatoren untersucht, die zu Synchronisation führen können. Aufbauend auf die Fragestellungen vorangegangener Arbeiten werden mit Hilfe theoretischer und experimenteller Studien sowie mit Hilfe numerischer Simulationen die Elemente der Tonentstehung in der Orgelpfeife und die Mechanismen der gegenseitigen Wechselwirkung von Orgelpfeifen identifiziert. Daraus wird erstmalig ein vollständig auf den aeroakustischen und fluiddynamischen Grundprinzipien basierendes nichtlinear gekoppeltes Modell selbst-erregter Oszillatoren für die Beschreibung des Verhaltens zweier wechselwirkender Orgelpfeifen entwickelt. Die durchgeführten Modellrechnungen werden mit den experimentellen Befunden verglichen. Es zeigt sich, dass die Tonentstehung und die Kopplungsmechanismen von Orgelpfeifen durch das entwickelte Oszillatormodell in weiten Teilen richtig beschrieben werden. Insbesondere kann damit die Ursache für den nichtlinearen Zusammenhang von Kopplungsstärke und Synchronisation des gekoppelten Zwei-Pfeifen Systems, welcher sich in einem nichtlinearen Verlauf der Arnoldzunge darstellt, geklärt werden. Mit den gewonnenen Erkenntnissen wird der Einfluss des Raumes auf die Tonentstehung bei Orgelpfeifen betrachtet. Dafür werden numerische Simulationen der Wechselwirkung einer Orgelpfeife mit verschiedenen Raumgeometrien, wie z. B. ebene, konvexe, konkave, und gezahnte Geometrien, exemplarisch untersucht. Auch der Einfluss von Schwellkästen auf die Tonentstehung und die Klangbildung der Orgelpfeife wird studiert. In weiteren, neuartigen Synchronisationsexperimenten mit identisch gestimmten Orgelpfeifen, sowie mit Mixturen wird die Synchronisation für verschiedene, horizontale und vertikale Pfeifenabstände in der Ebene der Schallabstrahlung, untersucht. Die dabei erstmalig beobachteten räumlich isotropen Unstetigkeiten im Schwingungsverhalten der gekoppelten Pfeifensysteme, deuten auf abstandsabhängige Wechsel zwischen gegen- und gleichphasigen Sychronisationsregimen hin. Abschließend wird die Möglichkeit dokumentiert, das Phänomen der Synchronisation zweier Orgelpfeifen durch numerische Simulationen, also der Behandlung der kompressiblen Navier-Stokes Gleichungen mit entsprechenden Rand- und Anfangsbedingungen, realitätsnah abzubilden. Auch dies stellt ein Novum dar.
The echo chamber model describes the development of groups in heterogeneous social networks. By heterogeneous social network we mean a set of individuals, each of whom represents exactly one opinion. The existing relationships between individuals can then be represented by a graph. The echo chamber model is a time-discrete model which, like a board game, is played in rounds. In each round, an existing relationship is randomly and uniformly selected from the network and the two connected individuals interact. If the opinions of the individuals involved are sufficiently similar, they continue to move closer together in their opinions, whereas in the case of opinions that are too far apart, they break off their relationship and one of the individuals seeks a new relationship. In this paper we examine the building blocks of this model. We start from the observation that changes in the structure of relationships in the network can be described by a system of interacting particles in a more abstract space.
These reflections lead to the definition of a new abstract graph that encompasses all possible relational configurations of the social network. This provides us with the geometric understanding necessary to analyse the dynamic components of the echo chamber model in Part III. As a first step, in Part 7, we leave aside the opinions of the inidividuals and assume that the position of the edges changes with each move as described above, in order to obtain a basic understanding of the underlying dynamics. Using Markov chain theory, we find upper bounds on the speed of convergence of an associated Markov chain to its unique stationary distribution and show that there are mutually identifiable networks that are not apparent in the dynamics under analysis, in the sense that the stationary distribution of the associated Markov chain gives equal weight to these networks.
In the reversible cases, we focus in particular on the explicit form of the stationary distribution as well as on the lower bounds of the Cheeger constant to describe the convergence speed.
The final result of Section 8, based on absorbing Markov chains, shows that in a reduced version of the echo chamber model, a hierarchical structure of the number of conflicting relations can be identified.
We can use this structure to determine an upper bound on the expected absorption time, using a quasi-stationary distribution. This hierarchy of structure also provides a bridge to classical theories of pure death processes. We conclude by showing how future research can exploit this link and by discussing the importance of the results as building blocks for a full theoretical understanding of the echo chamber model. Finally, Part IV presents a published paper on the birth-death process with partial catastrophe. The paper is based on the explicit calculation of the first moment of a catastrophe. This first part is entirely based on an analytical approach to second degree recurrences with linear coefficients. The convergence to 0 of the resulting sequence as well as the speed of convergence are proved. On the other hand, the determination of the upper bounds of the expected value of the population size as well as its variance and the difference between the determined upper bound and the actual value of the expected value. For these results we use almost exclusively the theory of ordinary nonlinear differential equations.
Hardy inequalities on graphs
(2024)
The dissertation deals with a central inequality of non-linear potential theory, the Hardy inequality. It states that the non-linear energy functional can be estimated from below by a pth power of a weighted p-norm, p>1. The energy functional consists of a divergence part and an arbitrary potential part. Locally summable infinite graphs were chosen as the underlying space. Previous publications on Hardy inequalities on graphs have mainly considered the special case p=2, or locally finite graphs without a potential part.
Two fundamental questions now arise quite naturally: For which graphs is there a Hardy inequality at all? And, if it exists, is there a way to obtain an optimal weight? Answers to these questions are given in Theorem 10.1 and Theorem 12.1. Theorem 10.1 gives a number of characterizations; among others, there is a Hardy inequality on a graph if and only if there is a Green's function. Theorem 12.1 gives an explicit formula to compute optimal Hardy weights for locally finite graphs under some additional technical assumptions. Examples show that Green's functions are good candidates to be used in the formula.
Emphasis is also placed on illustrating the theory with examples. The focus is on natural numbers, Euclidean lattices, trees and star graphs. Finally, a non-linear version of the Heisenberg uncertainty principle and a Rellich inequality are derived from the Hardy inequality.
Molecules are often naturally embedded in a complex environment. As a consequence, characteristic properties of a molecular subsystem can be substantially altered or new properties emerge due to interactions between molecular and environmental degrees of freedom. The present thesis is concerned with the numerical study of quantum dynamical and stationary properties of molecular vibrational systems embedded in selected complex environments.
In the first part, we discuss "strong-coupling" model scenarios for molecular vibrations interacting with few quantized electromagnetic field modes of an optical Fabry-Pérot cavity. We thoroughly elaborate on properties of emerging "vibrational polariton" light-matter hybrid states and examine the relevance of the dipole self-energy. Further, we identify cavity-induced quantum effects and an emergent dynamical resonance in a cavity-altered thermal isomerization model, which lead to significant suppression of thermal reaction rates. Moreover, for a single rovibrating diatomic molecule in an optical cavity, we observe non-adiabatic signatures in dynamics due to "vibro-polaritonic conical intersections" and discuss spectroscopically accessible "rovibro-polaritonic" light-matter hybrid states.
In the second part, we study a weakly coupled but numerically challenging quantum mechanical adsorbate-surface model system comprising a few thousand surface modes. We introduce an efficient construction scheme for a "hierarchical effective mode" approach to reduce the number of surface modes in a controlled manner. In combination with the multilayer multiconfigurational time-dependent Hartree (ML-MCTDH) method, we examine the vibrational adsorbate relaxation dynamics from different excited adsorbate states by solving the full non-Markovian system-bath dynamics for the characteristic relaxation time scale. We examine half-lifetime scaling laws from vibrational populations and identify prominent non-Markovian signatures as deviations from Markovian reduced system density matrix theory in vibrational coherences, system-bath entanglement and energy transfer dynamics.
In the final part of this thesis, we approach the dynamics and spectroscopy of vibronic model systems at finite temperature by formulating the ML-MCTDH method in the non-stochastic framework of thermofield dynamics. We apply our method to thermally-altered ultrafast internal conversion in the well-known vibronic coupling model of pyrazine. Numerically beneficial representations of multilayer wave functions ("ML-trees") are identified for different temperature regimes, which allow us to access thermal effects on both electronic and vibrational dynamics as well as spectroscopic properties for several pyrazine models.
This dissertation examines the activity of knowledge sharing by public employees in the workplace. Building on the Rubicon model of human behavior formation, I use a threefold approach to analyze the knowledge-sharing process: public employees’ motivation to share knowledge, their intention to share, and knowledge sharing behavior as such. The first article maps the knowledge-sharing behavior of public employees. It builds a typology of behavioral patterns and shows that public employees mainly share their knowledge responsively and directly with a knowledge receiver rather than an information medium. The second article elaborates on the construct of knowledge-sharing motivation and develops a scale to measure this kind of work motivation in a selective and domain-specific way. Data from three studies indicate three dimensions of knowledge-sharing motivation, namely appreciation, growth and altruism, and tangible rewards. Based on these dimensions, the third article analyzes whether the satisfaction of public employees’ underlying needs can foster ther knowledge-sharing intention. The study indicates that both tested treatments (appreciation by co-workers, benefits in a performance appraisal) positively affect knowledge-sharing intention if it is explicit knowledge that ought to be shared. However, no effects of either treatment can be found if implicit knowledge is shared. Hence, to foster sharing of explicit knowledge, the analyzed motivation-enhancing rewards can be used in public management practice. To enhance implicit knowledge sharing, ability- and opportunity-enhancing management instruments are discussed. All in all, this dissertation integrates a micro-level perspective on human knowledge sharing into a meso-level perspective on organizational knowledge management. It adds to the literature on workplace behaviors of public employees and knowledge management and aims to incorporate knowledge sharing and management into the public administration and management literature.
More than a century ago the phenomenon of non-Mendelian inheritance (NMI), defined as any type of inheritance pattern in which traits do not segregate in accordance with Mendel’s laws, was first reported. In the plant kingdom three genomic compartments, the nucleus, chloroplast, and mitochondrion, can participate in such a phenomenon. High-throughput sequencing (HTS) proved to be a key technology to investigate NMI phenomena by assembling and/or resequencing entire genomes. However, generation, analysis and interpretation of such datasets remain challenging by the multi-layered biological complexity. To advance our knowledge in the field of NMI, I conducted three studies involving different HTS technologies and implemented two new algorithms to analyze them.
In the first study I implemented a novel post-assembly pipeline, called Semi-Automated Graph-Based Assembly Curator (SAGBAC), which visualizes non-graph-based assemblies as graphs, identifies recombinogenic repeat pairs (RRPs), and reconstructs plant mitochondrial genomes (PMG) in a semiautomated workflow. We applied this pipeline to assemblies of three Oenothera species resulting in a spatially folded and circularized model. This model was confirmed by PCR and Southern blot analyses and was used to predict a defined set of 70 PMG isoforms. With Illumina Mate Pair and PacBio RSII data, the stoichiometry of the RRPs was determined quantitatively differing up to three-fold.
In the second study I developed a post-multiple sequence alignment algorithm, called correlation mapping (CM), which correlates segment-wise numbers of nucleotide changes to a numeric ascertainable phenotype. We applied this algorithm to 14 wild type and 18 mutagenized plastome assemblies within the Oenothera genus and identified two genes, accD and ycf2 that may cause the competitive behavior of plastid genotypes as plastids can be biparental inherited in Oenothera. Moreover, lipid composition of the plastid envelope membrane is affected by polymorphisms within these two genes.
For the third study, I programmed a pipeline to investigate a NMI phenomenon, known as paramutation, in tomato by analyzing DNA and bisulfite sequencing data as well as microarray data. We identified the responsible gene (Solyc02g0005200) and were able to fully repress its caused phenotype by heterologous complementation with a paramutation insensitive transgene of the Arabidopsis thaliana orthologue. Additionally, a suppressor mutant shows a globally altered DNA methylation pattern and carries a large deletion leading to a gene fusion involving a histone deacetylase.
In conclusion, my developed and implemented algorithms and data analysis pipelines are suitable to investigate NMI and led to novel insights about such phenomena by reconstructing PMGs (SAGBAC) as a requirement to study mitochondria-associated phenotypes, by identifying genes (CM) causing interplastidial competition as well by applying a DNA/Bisulfite-seq analysis pipeline to shed light in a transgenerational epigenetic inheritance phenomenon.
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.
Gegenstand der Arbeit ist die Beanspruchungssituation des Pflegepersonals im Krankenhausbereich. Es wird der Frage nachgegangen, mit welchem Verhaltens- und Erlebensmuster Pflegepersonen ihren Anforderungen gegenübertreten und wie sie über die Art und Weise der persönlichen Auseinandersetzung mit den Anforderungen ihre Beanspruchungsverhältnisse mitgestalten.Den theoretischen Ausgangspunkt der Arbeit bilden salutogenetisch orientierte Ressourcenmodelle, insbesondere Beckers Modell der seelischen Gesundheit (Becker, 1982, 1986). Nach ihm hängt der Gesundheitszustand einer Person davon ab, wie gut es ihr gelingt, externe und interne Anforderungen mithilfe externer und interner Ressourcen zu bewältigen. Hier knüpft das in der Arbeit im Mittelpunkt stehende diagnostische Instrument AVEM (Arbeitsbezogenes Verhaltens- und Erlebensmuster; Schaarschmidt & Fischer, 1996, 2001) an, das die Erfassung interner Anforderungen und Ressourcen der Person sowie deren Zuordnung zu 4 Verhaltens- und Erlebensmustern gegenüber der Arbeit unter Gesundheits- und Motivationsbezug ermöglicht.Mit den Hypothesen wird angenommen, dass in Anbetracht der problematischen Arbeitsbedingungen in der Pflege eine Zurücknahme im Engagement bzw. eine Schutzhaltung vor nicht gewollten und als unangemessen empfundenen Anforderungen sowie wenig beeinflussbaren Bedingungen im Vordergrund stehen. Dort, wo zumindest partiell gesundheitsförderliche und als herausfordernd erlebte Arbeitsbedingungen anzutreffen sind, sollten günstigere Musterkonstellationen auftreten. Wir vermuteten, dass sich die ungünstigen Tendenzen bereits in der Berufsausbildung und in frühen Berufsjahren zeigen. Musterveränderungen in gesundheits- und persönlichkeitsförderlicher Hinsicht sollten durch gezielte Intervention herbeigeführt werden können. Schließlich nahmen wir an, dass die Tätigkeit und die mit ihr verbundenen Anforderungen und Ausführungsbedingungen musterspezifisch wahrgenommen werden.Zur Beantwortung der Fragen werden Ergebnisse aus verschiedenen Quer- und Längsschnittuntersuchungen herangezogen, die in Wiener Spitälern und Krankenpflegeschulen, aber auch in deutschen Krankenhäusern durchgeführt wurden. Zu Vergleichszwecken werden Befunde anderer Berufsgruppen dargestellt. Neben dem AVEM wurden weitere Fragebögen zu folgenden Inhalten eingesetzt: Arbeitsbezogene Werte, Erleben von Ressourcen in der Pflegetätigkeit, Belastungserleben und Objektive Merkmale der Arbeitstätigkeit.Die Ergebnisse bestätigen die Hypothesen in allen wesentlichen Punkten. Im Vergleich mit anderen Berufsgruppen fallen für die Pflegekräfte deutliche Einschränkungen im Arbeitsengagement auf. In Bezug auf die gesundheitlichen Risikomuster nimmt das Pflegepersonal eine Mittelstellung ein. Die Musterdifferenzierung in der Pflegepopulation lässt die stärksten Unterschiede in Abhängigkeit von der Position erkennen: Je höher die Position, desto größer ist der Anteil des Gesundheitsmusters und desto geringer ist die Resignationstendenz. Die meisten Risikomuster zeigen sich bei den Pflegekräften mit der niedrigsten Qualifikation. Für Pflegeschüler ist ein zeitweiliges starkes Auftreten von resignativen Verhaltens- und Erlebensweisen sowie eine kontinuierliche Abnahme des Engagements kennzeichnend. Dieser Trend setzt sich nach Aufnahme der Berufstätigkeit fort. Nur gezielte intensive personenorientierte Interventionen erwiesen sich als geeignet, Musterveränderungen in gesundheits- und persönlichkeitsförderlicher Hinsicht zu erreichen. Die Tätigkeit und die mit ihr verbundenen Anforderungen und Ausführungsbedingungen werden musterspezifisch wahrgenommen, wobei Personen mit eingeschränktem Engagement bzw. mit einer Resignationstendenz wesentliche Tätigkeitsmerkmale, denen persönlichkeits- und gesundheitsförderliche Wirkung zugesprochen wird, für sich als wenig wichtig beurteilen und sich mehr Defizite im Verhalten gegenüber Patienten bescheinigen.Die Ergebnisse verweisen darauf, dass im Pflegeberuf vor allem die Zurückhaltung im Engagement Anlass für eine kritische Betrachtung sein muss. Das Problem "Burnout" stellt sich in seiner Bedeutung relativiert dar. Günstigere Voraussetzungen für die Aufrechterhaltung und Förderung der Gesundheit bestehen dort, wo im konkreten Arbeitsfeld ein erweiterter Tätigkeits- und Handlungsspielraum sowie mehr Verantwortung vorliegen. Diese Befunde stehen in Einklang mit arbeitspsychologischen Ressourcenmodellen. Die Befunde zu den Pflegeschülern verweisen auf teilweise ungünstige Eignungsvoraussetzungen der Auszubildenden und legen nahe, die Angemessenheit der Anforderungen in den Krankenpflegeschulen zu hinterfragen. Hinsichtlich der Möglichkeiten der Veränderung der Muster in gesundheits- und motivationsdienlicher Weise brachten die Ergebnisse zum Ausdruck, dass verhaltensbezogenen Maßnahmen ohne gleichzeitige bedingungsbezogene Interventionen wenig Erfolg beschieden ist. Mit Blick auf die musterspezifische Wahrnehmung der Tätigkeit und der mit ihr verbundenen Anforderungen und Ausführungsbedingungen ist schließlich grundsätzlich festzuhalten, dass arbeitspsychologische Konzepte, die hohen bzw. komplexen Anforderungen und umfangreichen Freiheitsgraden in der Arbeit grundsätzlich persönlichkeits- und gesundheitsförderliche Wirkungen zuschreiben, einer Relativierung durch eine differentielle Perspektive bedürfen. Die vorgefundene Interaktion von Persönlichkeit und Arbeitsbedingungen hat zur Konsequenz, dass Verhaltens- und Verhältnisprävention in untrennbarem Zusammenhang gesehen werden sollten.