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Galaxy clusters are the largest known gravitationally bound objects, their study is important for both an intrinsic understanding of their systems and an investigation of the large scale structure of the universe. The multi- component nature of galaxy clusters offers multiple observable signals across the electromagnetic spectrum. At X-ray wavelengths, galaxy clusters are simply identified as X-ray luminous, spatially extended, and extragalactic sources. X-ray observations offer the most powerful technique for constructing cluster catalogues. The main advantages of the X-ray cluster surveys are their excellent purity and completeness and the X-ray observables are tightly correlated with mass, which is indeed the most fundamental parameter of clusters. In my thesis I have conducted the 2XMMi/SDSS galaxy cluster survey, which is a serendipitous search for galaxy clusters based on the X-ray extended sources in the XMM-Newton Serendipitous Source Catalogue (2XMMi-DR3). The main aims of the survey are to identify new X-ray galaxy clusters, investigate their X-ray scaling relations, identify distant cluster candidates, and study the correlation of the X-ray and optical properties. The survey is constrained to those extended sources that are in the footprint of the Sloan Digital Sky Survey (SDSS) in order to be able to identify the optical counterparts as well as to measure their redshifts that are mandatory to measure their physical properties. The overlap area be- tween the XMM-Newton fields and the SDSS-DR7 imaging, the latest SDSS data release at the starting of the survey, is 210 deg^2. The survey comprises 1180 X-ray cluster candidates with at least 80 background-subtracted photon counts, which passed the quality control process. To measure the optical redshifts of the X-ray cluster candidates, I used three procedures; (i) cross-matching these candidates with the recent and largest optically selected cluster catalogues in the literature, which yielded the photometric redshifts of about a quarter of the X-ray cluster candidates. (ii) I developed a finding algorithm to search for overdensities of galaxies at the positions of the X-ray cluster candidates in the photometric redshift space and to measure their redshifts from the SDSS-DR8 data, which provided the photometric redshifts of 530 groups/clusters. (iii) I developed an algorithm to identify the cluster candidates associated with spectroscopically targeted Luminous Red Galaxies (LRGs) in the SDSS-DR9 and to measure the cluster spectroscopic redshift, which provided 324 groups and clusters with spectroscopic confirmation based on spectroscopic redshift of at least one LRG. In total, the optically confirmed cluster sample comprises 574 groups and clusters with redshifts (0.03 ≤ z ≤ 0.77), which is the largest X-ray selected cluster catalogue to date based on observations from the current X-ray observatories (XMM-Newton, Chandra, Suzaku, and Swift/XRT). Among the cluster sample, about 75 percent are newly X-ray discovered groups/clusters and 40 percent are new systems to the literature. To determine the X-ray properties of the optically confirmed cluster sample, I reduced and analysed their X-ray data in an automated way following the standard pipelines of processing the XMM-Newton data. In this analysis, I extracted the cluster spectra from EPIC(PN, MOS1, MOS2) images within an optimal aperture chosen to maximise the signal-to-noise ratio. The spectral fitting procedure provided the X-ray temperatures kT (0.5 - 7.5 keV) for 345 systems that have good quality X-ray data. For all the optically confirmed cluster sample, I measured the physical properties L500 (0.5 x 10^42 – 1.2 x 10^45 erg s-1 ) and M500 (1.1 x 10^13 – 4.9 x 10^14 M⊙) from an iterative procedure using published scaling relations. The present X-ray detected groups and clusters are in the low and intermediate luminosity regimes apart from few luminous systems, thanks to the XMM-Newton sensitivity and the available XMM-Newton deep fields The optically confirmed cluster sample with measurements of redshift and X-ray properties can be used for various astrophysical applications. As a first application, I investigated the LX - T relation for the first time based on a large cluster sample of 345 systems with X-ray spectroscopic parameters drawn from a single survey. The current sample includes groups and clusters with wide ranges of redshifts, temperatures, and luminosities. The slope of the relation is consistent with the published ones of nearby clusters with higher temperatures and luminosities. The derived relation is still much steeper than that predicted by self-similar evolution. I also investigated the evolution of the slope and the scatter of the LX - T relation with the cluster redshift. After excluding the low luminosity groups, I found no significant changes of the slope and the intrinsic scatter of the relation with redshift when dividing the sample into three redshift bins. When including the low luminosity groups in the low redshift subsample, I found its LX - T relation becomes after than the relation of the intermediate and high redshift subsamples. As a second application of the optically confirmed cluster sample from our ongoing survey, I investigated the correlation between the cluster X-ray and the optical parameters that have been determined in a homogenous way. Firstly, I investigated the correlations between the BCG properties (absolute magnitude and optical luminosity) and the cluster global proper- ties (redshift and mass). Secondly, I computed the richness and the optical luminosity within R500 of a nearby subsample (z ≤ 0.42, with a complete membership detection from the SDSS data) with measured X-ray temperatures from our survey. The relation between the estimated optical luminosity and richness is also presented. Finally, the correlation between the cluster optical properties (richness and luminosity) and the cluster global properties (X-ray luminosity, temperature, mass) are investigated.
In this work, the development of temperature- and protein-responsive sensor materials based on biocompatible, inverse hydrogel opals (IHOs) is presented. With these materials, large biomolecules can be specifically recognised and the binding event visualised. The preparation of the IHOs was performed with a template process, for which monodisperse silica particles were vertically deposited onto glass slides as the first step. The obtained colloidal crystals with a thickness of 5 μm displayed opalescent reflections because of the uniform alignment of the colloids. As a second step, the template was embedded in a matrix consisting of biocompatible, thermoresponsive hydrogels. The comonomers were selected from the family of oligo(ethylene glycol)methacrylates. The monomer solution was injected into a polymerisation mould, which contained the colloidal crystals as a template. The space in-between the template particles was filled with the monomer solution and the hydrogel was cured via UV-polymerisation. The particles were chemically etched, which resulted in a porous inner structure. The uniform alignment of the pores and therefore the opalescent reflection were maintained, so these system were denoted as inverse hydrogel opals. A pore diameter of several hundred nanometres as well as interconnections between the pores should facilitate a diffusion of bigger (bio)molecules, which was always a challenge in the presented systems until now. The copolymer composition was chosen to result in a hydrogel collapse over 35 °C. All hydrogels showed pronounced swelling in water below the critical temperature. The incorporation of a reactive monomer with hydroxyl groups ensured a potential coupling group for the introduction of recognition units for analytes, e.g. proteins. As a test system, biotin as a recognition unit for avidin was coupled to the IHO via polymer-analogous Steglich esterification. The amount of accessible biotin was quantified with a colorimetric binding assay. When avidin was added to the biotinylated IHO, the wavelength of the opalescent reflection was significantly shifted and therefore the binding event was visualised. This effect is based on the change in swelling behaviour of the hydrogel after binding of the hydrophilic avidin, which is amplified by the thermoresponsive nature of the hydrogel. A swelling or shrinking of the pores induces a change in distance of the crystal planes, which are responsible for the colour of the reflection. With these findings, the possibility of creating sensor materials or additional biomolecules in the size range of avidin is given.
The Semantic Web provides information contained in the World Wide Web as machine-readable facts. In comparison to a keyword-based inquiry, semantic search enables a more sophisticated exploration of web documents. By clarifying the meaning behind entities, search results are more precise and the semantics simultaneously enable an exploration of semantic relationships. However, unlike keyword searches, a semantic entity-focused search requires that web documents are annotated with semantic representations of common words and named entities. Manual semantic annotation of (web) documents is time-consuming; in response, automatic annotation services have emerged in recent years. These annotation services take continuous text as input, detect important key terms and named entities and annotate them with semantic entities contained in widely used semantic knowledge bases, such as Freebase or DBpedia. Metadata of video documents require special attention. Semantic analysis approaches for continuous text cannot be applied, because information of a context in video documents originates from multiple sources possessing different reliabilities and characteristics. This thesis presents a semantic analysis approach consisting of a context model and a disambiguation algorithm for video metadata. The context model takes into account the characteristics of video metadata and derives a confidence value for each metadata item. The confidence value represents the level of correctness and ambiguity of the textual information of the metadata item. The lower the ambiguity and the higher the prospective correctness, the higher the confidence value. The metadata items derived from the video metadata are analyzed in a specific order from high to low confidence level. Previously analyzed metadata are used as reference points in the context for subsequent disambiguation. The contextually most relevant entity is identified by means of descriptive texts and semantic relationships to the context. The context is created dynamically for each metadata item, taking into account the confidence value and other characteristics. The proposed semantic analysis follows two hypotheses: metadata items of a context should be processed in descendent order of their confidence value, and the metadata that pertains to a context should be limited by content-based segmentation boundaries. The evaluation results support the proposed hypotheses and show increased recall and precision for annotated entities, especially for metadata that originates from sources with low reliability. The algorithms have been evaluated against several state-of-the-art annotation approaches. The presented semantic analysis process is integrated into a video analysis framework and has been successfully applied in several projects for the purpose of semantic video exploration of videos.
Introduction: Intestinal bacteria influence gut morphology by affecting epithelial cell proliferation, development of the lamina propria, villus length and crypt depth [1]. Gut microbiota-derived factors have been proposed to also play a role in the development of a 30 % longer intestine, that is characteristic of PRM/Alf mice compared to other mouse strains [2, 3]. Polyamines and SCFAs produced by gut bacteria are important growth factors, which possibly influence mucosal morphology, in particular villus length and crypt depth and play a role in gut lengthening in the PRM/Alf mouse. However, experimental evidence is lacking. Aim: The objective of this work was to clarify the role of bacterially-produced polyamines on crypt depth, mucosa thickness and epithelial cell proliferation. For this purpose, C3H mice associated with a simplified human microbiota (SIHUMI) were compared with mice colonized with SIHUMI complemented by the polyamine-producing Fusobacterium varium (SIHUMI + Fv). In addition, the microbial impact on gut lengthening in PRM/Alf mice was characterized and the contribution of SCFAs and polyamines to this phenotype was examined. Results: SIHUMI + Fv mice exhibited an up to 1.7 fold higher intestinal polyamine concentration compared to SIHUMI mice, which was mainly due to increased putrescine concentrations. However, no differences were observed in crypt depth, mucosa thickness and epithelial proliferation. In PRM/Alf mice, the intestine of conventional mice was 8.5 % longer compared to germfree mice. In contrast, intestinal lengths of C3H mice were similar, independent of the colonization status. The comparison of PRM/Alf and C3H mice, both associated with SIHUMI + Fv, demonstrated that PRM/Alf mice had a 35.9 % longer intestine than C3H mice. However, intestinal SCFA and polyamine concentrations of PRM/Alf mice were similar or even lower, except N acetylcadaverine, which was 3.1-fold higher in PRM/Alf mice. When germfree PRM/Alf mice were associated with a complex PRM/Alf microbiota, the intestine was one quarter longer compared to PRM/Alf mice colonized with a C3H microbiota. This gut elongation correlated with levels of the polyamine N acetylspermine. Conclusion: The intestinal microbiota is able to influence intestinal length dependent on microbial composition and on the mouse genotype. Although SCFAs do not contribute to gut elongation, an influence of the polyamines N acetylcadaverine and N acetylspermine is conceivable. In addition, the study clearly demonstrated that bacterial putrescine does not influence gut morphology in C3H mice.
Kultur gibt den Menschen eine Orientierung. Sie machen darin ganz spezifische Erfahrungen. Hieraus entwickeln sich auch motivationale Orientierungen. Dadurch werden andere Erfahrungen gemacht, die Sportler können andere Motivation und Volition entwickeln. Dabei sind mehr kollektivistische Kulturen eher vermeidungs-motiviert und mehr individualistische Kulturen mehr erfolgsorientiert. Beim Kollektivismus erscheint die Leistungsmotivation eher unter einem sozialen Aspekt, nämlich die Auseinandersetzung mit einem Gütemaßstab, der eher von außen vorgegeben wird und weniger einem ausschließlich eigenen Maßstab. Ägypten erweist sich im Vergleich zu Deutschland als eine eher kollektivistisch geprägte Kultur. Daraus ergeben sich folgende Unterschiede: Einen signifikanten Unterschied zwischen deutschen und ägyptischen Ringern gibt es in der Wettkampforientierung und bei der Sieg- bzw. Gewinn-Orientierung. Die ägyptischen Ringer habe eine höhere Ausprägung als die Deutschen. Sie weisen auch eine etwas höhere Zielorientierung auf als die Deutschen. Entgegen den Erwartungen zeigte sich, dass es keine signifikanten Unterschiede zwischen den ägyptischen und deutschen Ringern gibt in der Variable: Sieg- bzw. Gewinn-Orientierung. Die Furcht vor Misserfolg sowie auch die Hoffnung auf Erfolg liegen höher bei den Ägyptern als bei den Deutschen. Bezogen auf die Modi der Handlungskontrolle verfügen die Deutschen Ringer über eine höher Ausprägung auf allen drei Komponenten. Sie haben eine höhere Handlungsorientierung nach Misserfolg, eine höhere Handlungsplanung sowie eine höhere Handlungstätigkeitsausführung. Diese kulturell kontrastive Studie über die psychologischen Aspekte, im Bereich der Leistungsmotivation und der Handlungskontrolle, kann für die Sportart Ringen sehr nützlich werden, da sie sehr wichtig ist beim Erkennen der sportlichen Überlegenheits- und Schwächemerkmale. Sie wiederspiegelt auch die Hochstimmung in den entwickelten Staaten oder die Misere in den anderen Staaten. Aus den interkulturellen Unterschieden in der Motivation und Volition können somit verschiedene Maßnahmen zu sportpsychologischen Interventionen entwickelt werden. Es sollte unbedingt darauf wert gelegt werden, dass die kulturell bedingten Unterschiede im Trainingsalltag beachtet werden, bei Teams, die aus Personen aus unterschiedlichen Kulturkreisen stammen.
The surface heat flow (qs) is paramount for modeling the thermal structure of the lithosphere. Changes in the qs over a distinct lithospheric unit are normally directly reflecting changes in the crustal composition and therewith the radiogenic heat budget (e.g., Rudnick et al., 1998; Förster and Förster, 2000; Mareschal and Jaupart, 2004; Perry et al., 2006; Hasterok and Chapman, 2011, and references therein) or, less usual, changes in the mantle heat flow (e.g., Pollack and Chapman, 1977). Knowledge of this physical property is therefore of great interest for both academic research and the energy industry. The present study focuses on the qs of central and southern Israel as part of the Sinai Microplate (SM). Having formed during Oligocene to Miocene rifting and break-up of the African and Arabian plates, the SM is characterized by a young and complex tectonic history. Resulting from the time thermal diffusion needs to pass through the lithosphere, on the order of several tens-of-millions of years (e.g., Fowler, 1990); qs-values of the area reflect conditions of pre-Oligocene times. The thermal structure of the lithosphere beneath the SM in general, and south-central Israel in particular, has remained poorly understood. To address this problem, the two parameters needed for the qs determination were investigated. Temperature measurements were made at ten pre-existing oil and water exploration wells, and the thermal conductivity of 240 drill core and outcrop samples was measured in the lab. The thermal conductivity is the sensitive parameter in this determination. Lab measurements were performed on both, dry and water-saturated samples, which is labor- and time-consuming. Another possibility is the measurement of thermal conductivity in dry state and the conversion to a saturated value by using mean model approaches. The availability of a voluminous and diverse dataset of thermal conductivity values in this study allowed (1) in connection with the temperature gradient to calculate new reliable qs values and to use them to model the thermal pattern of the crust in south-central Israel, prior to young tectonic events, and (2) in connection with comparable datasets, controlling the quality of different mean model approaches for indirect determination of bulk thermal conductivity (BTC) of rocks. The reliability of numerically derived BTC values appears to vary between different mean models, and is also strongly dependent upon sample lithology. Yet, correction algorithms may significantly reduce the mismatch between measured and calculated conductivity values based on the different mean models. Furthermore, the dataset allowed the derivation of lithotype-specific conversion equations to calculate the water-saturated BTC directly from data of dry-measured BTC and porosity (e.g., well log derived porosity) with no use of any mean model and thus provide a suitable tool for fast analysis of large datasets. The results of the study indicate that the qs in the study area is significantly higher than previously assumed. The new presented qs values range between 50 and 62 mW m⁻². A weak trend of decreasing heat flow can be identified from the east to the west (55-50 mW m⁻²), and an increase from the Dead Sea Basin to the south (55-62 mW m⁻²). The observed range can be explained by variation in the composition (heat production) of the upper crust, accompanied by more systematic spatial changes in its thickness. The new qs data then can be used, in conjunction with petrophysical data and information on the structure and composition of the lithosphere, to adjust a model of the pre-Oligocene thermal state of the crust in south-central Israel. The 2-D steady-state temperature model was calculated along an E-W traverse based on the DESIRE seismic profile (Mechie et al., 2009). The model comprises the entire lithosphere down to the lithosphere–asthenosphere boundary (LAB) involving the most recent knowledge of the lithosphere in pre-Oligocene time, i.e., prior to the onset of rifting and plume-related lithospheric thermal perturbations. The adjustment of modeled and measured qs allows conclusions about the pre-Oligocene LAB-depth. After the best fitting the most likely depth is 150 km which is consistent with estimations made in comparable regions of the Arabian Shield. It therefore comprises the first ever modelled pre-Oligocene LAB depth, and provides important clues on the thermal state of lithosphere before rifting. This, in turn, is vital for a better understanding of the (thermo)-dynamic processes associated with lithosphere extension and continental break-up.
Background: Increased numbers of intestinal E. coli are observed in inflammatory bowel disease, but the reasons for this proliferation and it exact role in intestinal inflammation are unknown. Aim of this PhD-project was to identify E. coli proteins involved in E. coli’s adaptation to the inflammatory conditions in the gut and to investigate whether these factors affect the host. Furthermore, the molecular basis for strain-specific differences between probiotic and harmful E. coli in their response to intestinal inflammation was investigated. Methods: Using mice monoassociated either with the adherent-invasive E. coli (AIEC) strain UNC or the probiotic E. coli Nissle, two different mouse models of intestinal inflammation were analysed: On the one hand, severe inflammation was induced by treating mice with 3.5% dextran sodium sulphate (DSS). On the other hand, a very mild intestinal inflammation was generated by associating interleukin 10-deficient (IL-10-/-) mice with E. coli. Differentially expressed proteins in the E. coli strains collected from caecal contents of these mice were identified by two-dimensional fluorescence difference gel electrophoresis. Results DSS-experiment: All DSS-treated mice revealed signs of a moderate caecal and a severe colonic inflammation. However, mice monoassociated with E. coli Nissle were less affected. In both E. coli strains, acute inflammation led to a downregulation of pathways involved in carbohydrate breakdown and energy generation. Accordingly, DSS-treated mice had lower caecal concentrations of bacterial fermentation products than the control mice. Differentially expressed proteins also included the Fe-S cluster repair protein NfuA, the tryptophanase TnaA, and the uncharacterised protein YggE. NfuA was upregulated nearly 3-fold in both E. coli strains after DSS administration. Reactive oxygen species produced during intestinal inflammation damage Fe-S clusters and thereby lead to an inactivation of Fe-S proteins. In vitro data indicated that the repair of Fe-S proteins by NfuA is a central mechanism in E. coli to survive oxidative stress. Expression of YggE, which has been reported to reduce the intracellular level of reactive oxygen species, was 4- to 8-fold higher in E. coli Nissle than in E. coli UNC under control and inflammatory conditions. In vitro growth experiments confirmed these results, indicating that E. coli Nissle is better equipped to cope with oxidative stress than E. coli UNC. Additionally, E. coli Nissle isolated from DSS-treated and control mice had TnaA levels 4- to 7-fold higher than E. coli UNC. In turn, caecal indole concentrations resulting from cleavage of tryptophan by TnaA were higher in E. coli Nissle- associated control mice than in the respective mice associated with E. coli UNC. Because of its anti-inflammatory effect, indole is hypothesised to be involved in the extension of the remission phase in ulcerative colitis described for E. coli Nissle. Results IL-10-/--experiment: Only IL-10-/- mice monoassociated with E. coli UNC for 8 weeks exhibited signs of a very mild caecal inflammation. In agreement with this weak inflammation, the variations in the bacterial proteome were small. Similar to the DSS-experiment, proteins downregulated by inflammation belong mainly to the central energy metabolism. In contrast to the DSS-experiment, no upregulation of chaperone proteins and NfuA were observed, indicating that these are strategies to overcome adverse effects of strong intestinal inflammation. The inhibitor of vertebrate C-type lysozyme, Ivy, was 2- to 3-fold upregulated on mRNA and protein level in E. coli Nissle in comparison to E. coli UNC isolated from IL-10-/- mice. By overexpressing ivy, it was demonstrated in vitro that Ivy contributes to a higher lysozyme resistance observed for E. coli Nissle, supporting the role of Ivy as a potential fitness factor in this E. coli strain. Conclusions: The results of this PhD-study demonstrate that intestinal bacteria sense even minimal changes in the health status of the host. While some bacterial adaptations to the inflammatory conditions are equal in response to strong and mild intestinal inflammation, other reactions are unique to a specific disease state. In addition, probiotic and colitogenic E. coli differ in their response to the intestinal inflammation and thereby may influence the host in different ways.
The main intention of the PhD project was to create a varve chronology for the Suigetsu Varves 2006' (SG06) composite profile from Lake Suigetsu (Japan) by thin section microscopy. The chronology was not only to provide an age-scale for the various palaeo-environmental proxies analysed within the SG06 project, but also and foremost to contribute, in combination with the SG06 14C chronology, to the international atmospheric radiocarbon calibration curve (IntCal). The SG06 14C data are based on terrestrial leaf fossils and therefore record atmospheric 14C values directly, avoiding the corrections necessary for the reservoir ages of the marine datasets, which are currently used beyond the tree-ring limit in the IntCal09 dataset (Reimer et al., 2009). The SG06 project is a follow up of the SG93 project (Kitagawa & van der Plicht, 2000), which aimed to produce an atmospheric calibration dataset, too, but suffered from incomplete core recovery and varve count uncertainties. For the SG06 project the complete Lake Suigetsu sediment sequence was recovered continuously, leaving the task to produce an improved varve count. Varve counting was carried out using a dual method approach utilizing thin section microscopy and micro X-Ray Fluorescence (µXRF). The latter was carried out by Dr. Michael Marshall in cooperation with the PhD candidate. The varve count covers 19 m of composite core, which corresponds to the time frame from ≈10 to ≈40 kyr BP. The count result showed that seasonal layers did not form in every year. Hence, the varve counts from either method were incomplete. This rather common problem in varve counting is usually solved by manual varve interpolation. But manual interpolation often suffers from subjectivity. Furthermore, sedimentation rate estimates (which are the basis for interpolation) are generally derived from neighbouring, well varved intervals. This assumes that the sedimentation rates in neighbouring intervals are identical to those in the incompletely varved section, which is not necessarily true. To overcome these problems a novel interpolation method was devised. It is computer based and automated (i.e. avoids subjectivity and ensures reproducibility) and derives the sedimentation rate estimate directly from the incompletely varved interval by statistically analysing distances between successive seasonal layers. Therefore, the interpolation approach is also suitable for sediments which do not contain well varved intervals. Another benefit of the novel method is that it provides objective interpolation error estimates. Interpolation results from the two counting methods were combined and the resulting chronology compared to the 14C chronology from Lake Suigetsu, calibrated with the tree-ring derived section of IntCal09 (which is considered accurate). The varve and 14C chronology showed a high degree of similarity, demonstrating that the novel interpolation method produces reliable results. In order to constrain the uncertainties of the varve chronology, especially the cumulative error estimates, U-Th dated speleothem data were used by linking the low frequency 14C signal of Lake Suigetsu and the speleothems, increasing the accuracy and precision of the Suigetsu calibration dataset. The resulting chronology also represents the age-scale for the various palaeo-environmental proxies analysed in the SG06 project. One proxy analysed within the PhD project was the distribution of event layers, which are often representatives of past floods or earthquakes. A detailed microfacies analysis revealed three different types of event layers, two of which are described here for the first time for the Suigetsu sediment. The types are: matrix supported layers produced as result of subaqueous slope failures, turbidites produced as result of landslides and turbidites produced as result of flood events. The former two are likely to have been triggered by earthquakes. The vast majority of event layers was related to floods (362 out of 369), which allowed the construction of a respective chronology for the last 40 kyr. Flood frequencies were highly variable, reaching their greatest values during the global sea level low-stand of the Glacial, their lowest values during Heinrich Event 1. Typhoons affecting the region represent the most likely control on the flood frequency, especially during the Glacial. However, also local, non-climatic controls are suggested by the data. In summary, the work presented here expands and revises knowledge on the Lake Suigetsu sediment and enabls the construction of a far more precise varve chronology. The 14C calibration dataset is the first such derived from lacustrine sediments to be included into the (next) IntCal dataset. References: Kitagawa & van der Plicht, 2000, Radiocarbon, Vol 42(3), 370-381 Reimer et al., 2009, Radiocarbon, Vol 51(4), 1111-1150
Within the course of this thesis, I have investigated the complex interplay between electron and lattice dynamics in nanostructures of perovskite oxides. Femtosecond hard X-ray pulses were utilized to probe the evolution of atomic rearrangement directly, which is driven by ultrafast optical excitation of electrons. The physics of complex materials with a large number of degrees of freedom can be interpreted once the exact fingerprint of ultrafast lattice dynamics in time-resolved X-ray diffraction experiments for a simple model system is well known. The motion of atoms in a crystal can be probed directly and in real-time by femtosecond pulses of hard X-ray radiation in a pump-probe scheme. In order to provide such ultrashort X-ray pulses, I have built up a laser-driven plasma X-ray source. The setup was extended by a stable goniometer, a two-dimensional X-ray detector and a cryogen-free cryostat. The data acquisition routines of the diffractometer for these ultrafast X-ray diffraction experiments were further improved in terms of signal-to-noise ratio and angular resolution. The implementation of a high-speed reciprocal-space mapping technique allowed for a two-dimensional structural analysis with femtosecond temporal resolution. I have studied the ultrafast lattice dynamics, namely the excitation and propagation of coherent phonons, in photoexcited thin films and superlattice structures of the metallic perovskite SrRuO3. Due to the quasi-instantaneous coupling of the lattice to the optically excited electrons in this material a spatially and temporally well-defined thermal stress profile is generated in SrRuO3. This enables understanding the effect of the resulting coherent lattice dynamics in time-resolved X-ray diffraction data in great detail, e.g. the appearance of a transient Bragg peak splitting in both thin films and superlattice structures of SrRuO3. In addition, a comprehensive simulation toolbox to calculate the ultrafast lattice dynamics and the resulting X-ray diffraction response in photoexcited one-dimensional crystalline structures was developed in this thesis work. With the powerful experimental and theoretical framework at hand, I have studied the excitation and propagation of coherent phonons in more complex material systems. In particular, I have revealed strongly localized charge carriers after above-bandgap femtosecond photoexcitation of the prototypical multiferroic BiFeO3, which are the origin of a quasi-instantaneous and spatially inhomogeneous stress that drives coherent phonons in a thin film of the multiferroic. In a structurally imperfect thin film of the ferroelectric Pb(Zr0.2Ti0.8)O3, the ultrafast reciprocal-space mapping technique was applied to follow a purely strain-induced change of mosaicity on a picosecond time scale. These results point to a strong coupling of in- and out-of-plane atomic motion exclusively mediated by structural defects.
This thesis proposes a privacy protection framework for the controlled distribution and use of personal private data. The framework is based on the idea that privacy policies can be set directly by the data owner and can be automatically enforced against the data user. Data privacy continues to be a very important topic, as our dependency on electronic communication maintains its current growth, and private data is shared between multiple devices, users and locations. The growing amount and the ubiquitous availability of personal private data increases the likelihood of data misuse. Early privacy protection techniques, such as anonymous email and payment systems have focused on data avoidance and anonymous use of services. They did not take into account that data sharing cannot be avoided when people participate in electronic communication scenarios that involve social interactions. This leads to a situation where data is shared widely and uncontrollably and in most cases the data owner has no control over further distribution and use of personal private data. Previous efforts to integrate privacy awareness into data processing workflows have focused on the extension of existing access control frameworks with privacy aware functions or have analysed specific individual problems such as the expressiveness of policy languages. So far, very few implementations of integrated privacy protection mechanisms exist and can be studied to prove their effectiveness for privacy protection. Second level issues that stem from practical application of the implemented mechanisms, such as usability, life-time data management and changes in trustworthiness have received very little attention so far, mainly because they require actual implementations to be studied. Most existing privacy protection schemes silently assume that it is the privilege of the data user to define the contract under which personal private data is released. Such an approach simplifies policy management and policy enforcement for the data user, but leaves the data owner with a binary decision to submit or withhold his or her personal data based on the provided policy. We wanted to empower the data owner to express his or her privacy preferences through privacy policies that follow the so-called Owner-Retained Access Control (ORAC) model. ORAC has been proposed by McCollum, et al. as an alternate access control mechanism that leaves the authority over access decisions by the originator of the data. The data owner is given control over the release policy for his or her personal data, and he or she can set permissions or restrictions according to individually perceived trust values. Such a policy needs to be expressed in a coherent way and must allow the deterministic policy evaluation by different entities. The privacy policy also needs to be communicated from the data owner to the data user, so that it can be enforced. Data and policy are stored together as a Protected Data Object that follows the Sticky Policy paradigm as defined by Mont, et al. and others. We developed a unique policy combination approach that takes usability aspects for the creation and maintenance of policies into consideration. Our privacy policy consists of three parts: A Default Policy provides basic privacy protection if no specific rules have been entered by the data owner. An Owner Policy part allows the customisation of the default policy by the data owner. And a so-called Safety Policy guarantees that the data owner cannot specify disadvantageous policies, which, for example, exclude him or her from further access to the private data. The combined evaluation of these three policy-parts yields the necessary access decision. The automatic enforcement of privacy policies in our protection framework is supported by a reference monitor implementation. We started our work with the development of a client-side protection mechanism that allows the enforcement of data-use restrictions after private data has been released to the data user. The client-side enforcement component for data-use policies is based on a modified Java Security Framework. Privacy policies are translated into corresponding Java permissions that can be automatically enforced by the Java Security Manager. When we later extended our work to implement server-side protection mechanisms, we found several drawbacks for the privacy enforcement through the Java Security Framework. We solved this problem by extending our reference monitor design to use Aspect-Oriented Programming (AOP) and the Java Reflection API to intercept data accesses in existing applications and provide a way to enforce data owner-defined privacy policies for business applications.
Low molecular weight organic acids (LMWOAs) are important nutrients for microbes. However, most LMWOAs do not exist freely in the environment but are bound to macromolecular organic matter, e.g. kerogen, lignite and coal. During burial and geological maturation of sedimentary macromolecular organic matter biological and abiological processes promote the liberation of LMWOAs into the surrounding sediment. Through this process, microbes in sedimentary subsurface environments are supplied with essential nutrients. To estimate the feedstock potential of buried macromolecular organic matter to many environments it is important to determine the amount of LMWOAs that are bound to such a matrix. However, high-pressure and high temperature are a key feature of deep subsurface environments, and these physical parameters have a profound influence on chemical reaction kinetics. Therefore it is essential for the estimation of the feedstock potential to generate high-pressure and high temperature for the liberation of LMWOAs to recreate true in-situ conditions. This work presents a newly developed, inexpensive incubation system for biological and geological samples. It allows the application of high-pressure and high temperature as well as a subsampling of the liquid phase without loss of pressure, thereby not disturbing the on-going processes. When simulating the liberation of LMWOAs from sedimentary organic matter, the newly developed incubation system produces more realistic results than other extraction systems like Soxhlet. The extraction products remain in the extraction medium throughout the extraction, influencing the chemical conditions of the extraction medium. Sub-bituminous coal samples from New Zealand as well as lignite samples from Germany were extracted at elevated temperature (90˚C) and pressure (5 MPa). The main LMWOAs released from these low rank coals were formate, acetate and oxalate. Extraction efficiency was increased by two to four times for formate, acetate and oxalate in comparison to existing extraction methods without pressurisation and with demineralised water. This shows the importance of pressure for the simulation of true in-situ conditions and suggests that the amount of bioavailable LMWOAs is higher than previously thought. With the increase in carbon capture and storage (CCS) and the enhanced recovery of oil and gas (EOR/EGR), more and more CO2 becomes injected into the underground. However, the effects of elevated concentrations of carbon dioxide on sedimentary organic matter are rarely investigated. As the incuabtion system allows the manipulation of the composition and partial pressure of dissolved gasses, the effect of highly gas-enriched (CO2, CO2/SO2, CO2/NO2; to simulate flue gas conditions) waters on the extraction yield of LMWOAs from macromolecular organic matter was evaluated. For sub-bituminous coal the concentrations of all LMWAOs decreased upon the addition of gas, irrespective of its composition, whereas for lignite formate always and acetate mostly increased, while oxalate decreased. This suggests an positive effect on the nutrient supply for the subsurface microbiota of lignite layers, as formate and acetate are the most common LMWOAs used for microbial metabolism. In terrestrial mud volcanoes (TMVs), sedimentary material is rapidly ascending from great depth to the surface. Therefore LMWOAs that were produced from buried macromolecular organic matter at depth are also brought up to the surface, and fuel heterotrophic microbial ecosystems at the surface. TMVs represent geochemically and microbiologically diverse habitats, which are supplied with organic substrates and electron acceptors from deep-seated hydrocarbon-generating systems and intersected shallow aquifers, respectively. The main electron donor in TMVs in Azerbaijan is sulphate, and microbial sulphate reduction leads to the production of a wide range of reduced sulphur species that are key players in several biological processes. In our study we estimated the effect of LMWOAs on the sulphur metabolising activity of microorganims in TMVs from Azerbaijan. The addition of a mixture of volatile fatty acids containing acetate and other LMWOAs showed significant positive response to the sulphate reduction rate (SRR) of samples of several mud volcanoes. Further investigations on the temperature dependency of the SRR and the characterisation of thermophilic sulphate-reducing bacteria (SRB) showed a connection between the deep hot subsurface and the surface.
In this work, thermosensitive hydrogels having tunable thermo-mechanical properties were synthesized. Generally the thermal transition of thermosensitive hydrogels is based on either a lower critical solution temperature (LCST) or critical micelle concentration/ temperature (CMC/ CMT). The temperature dependent transition from sol to gel with large volume change may be seen in the former type of thermosensitive hydrogels and is negligible in CMC/ CMT dependent systems. The change in volume leads to exclusion of water molecules, resulting in shrinking and stiffening of system above the transition temperature. The volume change can be undesired when cells are to be incorporated in the system. The gelation in the latter case is mainly driven by micelle formation above the transition temperature and further colloidal packing of micelles around the gelation temperature. As the gelation mainly depends on concentration of polymer, such a system could undergo fast dissolution upon addition of solvent. Here, it was envisioned to realize a thermosensitive gel based on two components, one responsible for a change in mechanical properties by formation of reversible netpoints upon heating without volume change, and second component conferring degradability on demand. As first component, an ABA triblockcopolymer (here: Poly(ethylene glycol)-b-poly(propylene glycol)-b-poly(ethylene glycol) (PEPE) with thermosensitive properties, whose sol-gel transition on the molecular level is based on micellization and colloidal jamming of the formed micelles was chosen, while for the additional macromolecular component crosslinking the formed micelles biopolymers were employed. The synthesis of the hydrogels was performed in two ways, either by physical mixing of compounds showing electrostatic interactions, or by covalent coupling of the components. Biopolymers (here: the polysaccharides hyaluronic acid, chondroitin sulphate, or pectin, as well as the protein gelatin) were employed as additional macromolecular crosslinker to simultaneously incorporate an enzyme responsiveness into the systems. In order to have strong ionic/electrostatic interactions between PEPE and polysaccharides, PEPE was aminated to yield predominantly mono- or di-substituted PEPEs. The systems based on aminated PEPE physically mixed with HA showed an enhancement in the mechanical properties such as, elastic modulus (G′) and viscous modulus (G′′) and a decrease of the gelation temperature (Tgel) compared to the PEPE at same concentration. Furthermore, by varying the amount of aminated PEPE in the composition, the Tgel of the system could be tailored to 27-36 °C. The physical mixtures of HA with di-amino PEPE (HA·di-PEPE) showed higher elastic moduli G′ and stability towards dissolution compared to the physical mixtures of HA with mono-amino PEPE (HA·mono-PEPE). This indicates a strong influence of electrostatic interaction between –COOH groups of HA and –NH2 groups of PEPE. The physical properties of HA with di-amino PEPE (HA·di-PEPE) compare beneficially with the physical properties of the human vitreous body, the systems are highly transparent, and have a comparable refractive index and viscosity. Therefore,this material was tested for a potential biological application and was shown to be non-cytotoxic in eluate and direct contact tests. The materials will in the future be investigated in further studies as vitreous body substitutes. In addition, enzymatic degradation of these hydrogels was performed using hyaluronidase to specifically degrade the HA. During the degradation of these hydrogels, increase in the Tgel was observed along with decrease in the mechanical properties. The aminated PEPE were further utilised in the covalent coupling to Pectin and chondroitin sulphate by using EDC as a coupling agent. Here, it was possible to adjust the Tgel (28-33 °C) by varying the grafting density of PEPE to the biopolymer. The grafting of PEPE to Pectin enhanced the thermal stability of the hydrogel. The Pec-g-PEPE hydrogels were degradable by enzymes with slight increase in Tgel and decrease in G′ during the degradation time. The covalent coupling of aminated PEPE to HA was performed by DMTMM as a coupling agent. This method of coupling was observed to be more efficient compared to EDC mediated coupling. Moreover, the purification of the final product was performed by ultrafiltration technique, which efficiently removed the unreacted PEPE from the final product, which was not sufficiently achieved by dialysis. Interestingly, the final products of these reaction were in a gel state and showed enhancement in the mechanical properties at very low concentrations (2.5 wt%) near body temperature. In these hydrogels the resulting increase in mechanical properties was due to the combined effect of micelle packing (physical interactions) by PEPE and covalent netpoints between PEPE and HA. PEPE alone or the physical mixtures of the same components were not able to show thermosensitive behavior at concentrations below 16 wt%. These thermosensitive hydrogels also showed on demand solubilisation by enzymatic degradation. The concept of thermosensitivity was introduced to 3D architectured porous hydrogels, by covalently grafting the PEPE to gelatin and crosslinking with LDI as a crosslinker. Here, the grafted PEPE resulted in a decrease in the helix formation in gelatin chains and after fixing the gelatin chains by crosslinking, the system showed an enhancement in the mechanical properties upon heating (34-42 °C) which was reversible upon cooling. A possible explanation of the reversible changes in mechanical properties is the strong physical interactions between micelles formed by PEPE being covalently linked to gelatin. Above the transition temperature, the local properties were evaluated by AFM indentation of pore walls in which an increase in elastic modulus (E) at higher temperature (37 °C) was observed. The water uptake of these thermosensitive architectured porous hydrogels was also influenced by PEPE and temperature (25 °C and 37 °C), showing lower water up take at higher temperature and vice versa. In addition, due to the lower water uptake at high temperature, the rate of hydrolytic degradation of these systems was found to be decreased when compared to pure gelatin architectured porous hydrogels. Such temperature sensitive architectured porous hydrogels could be important for e.g. stem cell culturing, cell differentiation and guided cell migration, etc. Altogether, it was possible to demonstrate that the crosslinking of micelles by a macromolecular crosslinker increased the shear moduli, viscosity, and stability towards dissolution of CMC-based gels. This effect could be likewise be realized by covalent or non-covalent mechanisms such as, micelle interactions, physical interactions of gelatin chains and physical interactions between gelatin chains and micelles. Moreover, the covalent grafting of PEPE will create additional net-points which also influence the mechanical properties of thermosensitive architectured porous hydrogels. Overall, the physical and chemical interactions and reversible physical interactions in such thermosensitive architectured porous hydrogels gave a control over the mechanical properties of such complex system. The hydrogels showing change of mechanical properties without a sol-gel transition or volume change are especially interesting for further study with cell proliferation and differentiation.
In der vorliegenden Arbeit werden verschiedene Spektrometer für die Analyse von Gasen bzw. Gasgemischen vorgestellt und deren Design, Aufbau, Charakterisierung und Optimierung beschrieben. Das Resultat der Optimierung und Weiterentwicklungen ist ein spektral breitbandiges Cavity-Ring-Down-Spektrometer (CRD-Spektrometer). Ausgangspunkt der hier vorgestellten Arbeit ist ein Spektrometer auf Basis klassischer Absorptionsspektroskopie in einer Multireflexionszelle. Für dieses Spektrometer wurde als Strahlquelle ein Superkontinuumlaser verwendet. Der Vorteil dieses Spektrometers liegt in seiner Kompaktheit. Mit diesem Spektrometer wurden Absorptionsspektren von mehreren Reingasen und einem Gasgemisch über einen Wellenlängenbereich von 1500 nm – 1700 nm aufgenommen. Der qualitative Vergleich mit zu erwartenden Spektren, welche auf der HITRAN-Datenbank basieren, zeigte eine gute Übereinstimmung. Die quantitative Interpretierbarkeit der Daten war jedoch stark eingeschränkt aufgrund des hohen zufälligen und systematischen Fehlers der Messungen. Als Konsequenz aus der als nicht zufriedenstellend bewerteten quantitativen Interpretierbarkeit der Daten wurde eine alternative Messmethode gesucht, welche eine höhere Sensitivität und Genauigkeit ermöglicht. Die Wahl fiel auf die Cavity-Ring-Down-Spektroskopie, eine resonatorgestützte Variante der Absorptionsspektroskopie. Wesentliche Vorteile dieser Technik sind a) die Unabhängigkeit von Leistungsschwankungen der Strahlquelle, b) ein effektiver Absorptionsweg von bis zu mehreren Kilometern, welcher sich unmittelbar auf die Sensitivität der Messungen auswirkt, c) die Ermittlung absoluter Absorberkonzentrationen, ohne die Notwendigkeit einer Kalibrierung oder den Vergleich mit einer Referenzzelle und d) die Vernachlässigbarkeit von Absorptionen außerhalb des Resonators. Als notwendiger Zwischenschritt auf dem Weg zu einem breitbandigen CRD-Spektrometer wurde zunächst ein monochromatisches CRD-Spektrometer designt, aufgebaut und charakterisiert. Für die effektive Einkopplung von Strahlungsenergie in einen Resonator ist die Anpassung der Strahlparameter an die Mode des Resonators notwendig. Voraussetzung dieser Anpassung ist die Kenntnis der Strahlparameter, welche experimentell ermittelt wurden. Im Laufe des Aufbaus des Spektrometers ergab sich, dass trotz der Modenanpassung die Einkopplung der Strahlungsenergie in den Resonator gestört wurde. Daraufhin wurden systematisch mögliche Ursachen dieser Störung untersucht und das Spektrometer optimiert. Mit diesem optimierten Spektrometer wurden Spektren gemessen, welche sowohl qualitativ als auch quantitativ gut mit den zu erwartenden Spektren übereinstimmen. Als Nachweisgrenze dieses Spektrometers wurde ein Wert für den Absorptionskoeffizienten alpha von 10^-8 cm-1 bestimmt. Mit dem monochromatischen CRD-Spektrometer war es zudem möglich, isotopenspezifische Messungen durchzuführen. Für das breitbandige Spektrometer wurde als Strahlquelle eine ASE-Diode (amplified spontaneous emission) verwendet. Dabei handelt es sich um eine inkohärente Strahlquelle. Mittels Messungen nach dem Prinzip der Cavity-Enhanced-Absorptionsspektroskopie wurde die generelle Funktionalität des resonatorgestützten Spektrometers überprüft. Anschließend wurden die wellenlängenabhängigen Abklingsignale des leeren und des mit einem CO2-Luft-Gemisch gefüllten Resonators gemessen und ebenfalls mit den zu erwartenden Spektren verglichen. Qualitativ stimmen die experimentellen Spektren gut mit den zu erwartenden Spektren überein. Für die quantitative Interpretation der Daten wurde ein spezieller Algorithmus entwickelt, der die spektrale Auflösung des Systems berücksichtigt. Mit dem vorgestellten Spektrometer ist so die qualitative und quantitative Interpretation der Spektren möglich. Die Nachweisgrenze des breitbandigen Cavity-Ring-Down-Spektrometers wurde zu einem Wert von alpha = 8x10^-7 cm-1 bestimmt. Der systematischen und der zufällige Fehler der Messungen lagen bei Werten von ca. 1%. Bei diesem Spektrometer handelt es sich um einen Prototyp. Mittels Optimierung des Systems lassen sich sowohl der Wert der Nachweisgrenze als auch die Fehler der Messungen verbessern.
Famously, Einstein read off the geometry of spacetime from Maxwell's equations. Today, we take this geometry that serious that our fundamental theory of matter, the standard model of particle physics, is based on it. However, it seems that there is a gap in our understanding if it comes to the physics outside of the solar system. Independent surveys show that we need concepts like dark matter and dark energy to make our models fit with the observations. But these concepts do not fit in the standard model of particle physics. To overcome this problem, at least, we have to be open to matter fields with kinematics and dynamics beyond the standard model. But these matter fields might then very well correspond to different spacetime geometries. This is the basis of this thesis: it studies the underlying spacetime geometries and ventures into the quantization of those matter fields independently of any background geometry. In the first part of this thesis, conditions are identified that a general tensorial geometry must fulfill to serve as a viable spacetime structure. Kinematics of massless and massive point particles on such geometries are introduced and the physical implications are investigated. Additionally, field equations for massive matter fields are constructed like for example a modified Dirac equation. In the second part, a background independent formulation of quantum field theory, the general boundary formulation, is reviewed. The general boundary formulation is then applied to the Unruh effect as a testing ground and first attempts are made to quantize massive matter fields on tensorial spacetimes.
In soils and sediments there is a strong coupling between local biogeochemical processes and the distribution of water, electron acceptors, acids and nutrients. Both sides are closely related and affect each other from small scale to larger scales. Soil structures such as aggregates, roots, layers or macropores enhance the patchiness of these distributions. At the same time it is difficult to access the spatial distribution and temporal dynamics of these parameter. Noninvasive imaging techniques with high spatial and temporal resolution overcome these limitations. And new non-invasive techniques are needed to study the dynamic interaction of plant roots with the surrounding soil, but also the complex physical and chemical processes in structured soils. In this study we developed an efficient non-destructive in-situ method to determine biogeochemical parameters relevant to plant roots growing in soil. This is a quantitative fluorescence imaging method suitable for visualizing the spatial and temporal pH changes around roots. We adapted the fluorescence imaging set-up and coupled it with neutron radiography to study simultaneously root growth, oxygen depletion by respiration activity and root water uptake. The combined set up was subsequently applied to a structured soil system to map the patchy structure of oxic and anoxic zones induced by a chemical oxygen consumption reaction for spatially varying water contents. Moreover, results from a similar fluorescence imaging technique for nitrate detection were complemented by a numerical modeling study where we used imaging data, aiming to simulate biodegradation under anaerobic, nitrate reducing conditions.
Diet is a major force influencing the intestinal microbiota. This is obvious from drastic changes in microbiota composition after a dietary alteration. Due to the complexity of the commensal microbiota and the high inter-individual variability, little is known about the bacterial response at the cellular level. The objective of this work was to identify mechanisms that enable gut bacteria to adapt to dietary factors. For this purpose, germ-free mice monoassociated with the commensal Escherichia coli K-12 strain MG1655 were fed three different diets over three weeks: a diet rich in starch, a diet rich in non-digestible lactose and a diet rich in casein. Two dimensional gel electrophoresis and electrospray tandem mass spectrometry were applied to identify differentially expressed proteins of E. coli recovered from small intestine and caecum of mice fed the lactose or casein diets in comparison with those of mice fed the starch diet. Selected differentially expressed bacterial proteins were characterised in vitro for their possible roles in bacterial adaptation to the various diets. Proteins belonging to the oxidative stress regulon oxyR such as alkyl hydroperoxide reductase subunit F (AhpF), DNA protection during starvation protein (Dps) and ferric uptake regulatory protein (Fur), which are required for E. coli’s oxidative stress response, were upregulated in E. coli of mice fed the lactose-rich diet. Reporter gene analysis revealed that not only oxidative stress but also carbohydrate-induced osmotic stress led to the OxyR-dependent expression of ahpCF and dps. Moreover, the growth of E. coli mutants lacking the ahpCF or oxyR genes was impaired in the presence of non-digestible sucrose. This indicates that some OxyR-dependent proteins are crucial for the adaptation of E. coli to osmotic stress conditions. In addition, the function of two so far poorly characterised E. coli proteins was analysed: 2 deoxy-D gluconate 3 dehydrogenase (KduD) was upregulated in intestinal E. coli of mice fed the lactose-rich diet and this enzyme and 5 keto 4 deoxyuronate isomerase (KduI) were downregulated on the casein-rich diet. Reporter gene analysis identified galacturonate and glucuronate as inducers of the kduD and kduI gene expression. Moreover, KduI was shown to facilitate the breakdown of these hexuronates, which are normally degraded by uronate isomerase (UxaC), altronate oxidoreductase (UxaB), altronate dehydratase (UxaA), mannonate oxidoreductase (UxuB) and mannonate dehydratase (UxuA), whose expression was repressed by osmotic stress. The growth of kduID-deficient E. coli on galacturonate or glucuronate was impaired in the presence of osmotic stress, suggesting KduI and KduD to compensate for the function of the regular hexuronate degrading enzymes under such conditions. This indicates a novel function of KduI and KduD in E. coli’s hexuronate metabolism. Promotion of the intracellular formation of hexuronates by lactose connects these in vitro observations with the induction of KduD on the lactose-rich diet. Taken together, this study demonstrates the crucial influence of osmotic stress on the gene expression of E. coli enzymes involved in stress response and metabolic processes. Therefore, the adaptation to diet-induced osmotic stress is a possible key factor for bacterial colonisation of the intestinal environment.
Rhythm is a temporal and systematic organization of acoustic events in terms of prominence, timing and grouping, helping to structure our most basic experiences, such as body movement, music and speech. In speech, rhythm groups auditory events, e.g., sounds and pauses, together into words, making their boundaries acoustically prominent and aiding word segmentation and recognition by the hearer. After word recognition, the hearer is able to retrieve word meaning form his mental lexicon, integrating it with information from other linguistic domains, such as semantics, syntax and pragmatics, until comprehension is achieved. The importance of speech rhythm, however, is not restricted to word segmentation and recognition only. Beyond the word level rhythm continues to operate as an organization device, interacting with different linguistic domains, such as syntax and semantics, and grouping words into larger prosodic constituents, organized in a prosodic hierarchy. This dissertation investigates the function of speech rhythm as a sentence segmentation device during syntactic ambiguity processing, possible limitations on its use, i.e., in the context of second language processing, and its transferability as cognitive skill to the music domain.
Inhibition, attentional control, and causes of forgetting in working memory: a formal approach
(2013)
In many cognitive activities, the temporary maintenance and manipulation of mental objects is a necessary step in order to reach a cognitive goal. Working memory has been regarded as the process responsible for those cognitive activities. This thesis addresses the question: what limits working-memory capacity (WMC)? A question that still remains controversial (Barrouillet & Camos, 2009; Lewandowsky, Oberauer, & Brown, 2009). This study attempted to answer this question by proposing that the dynamics between the causes of forgetting and the processes helping the maintenance, and the manipulation of the memoranda are the key aspects in understanding the limits of WMC.
Chapter 1 introduced key constructs and the strategy to examine the dynamics between inhibition, attentional control, and the causes of forgetting in working memory.
The study in Chapter 2 tested the performance of children, young adults, and old adults in a working-memory updating-task with two conditions: one condition included go steps and the other condition included go, and no-go steps. The interference model (IM; Oberauer & Kliegl, 2006), a model proposing interference-related mechanisms as the main cause of forgetting was used to simultaneously fit the data of these age groups. In addition to the interference-related parameters reflecting interference by feature overwriting and interference by confusion, and in addition to the parameters reflecting the speed of processing, the study included a new parameter that captured the time for switching between go steps and no-go steps. The study indicated that children and young adults were less susceptible than old adults to interference by feature overwriting; children were the most susceptible to interference by confusion, followed by old adults and then by young adults; young adults presented the higher rate of processing, followed by children and then by old adults; and young adults were the fastest group switching from go steps to no-go steps.
Chapter 3 examined the dynamics between causes of forgetting and the inhibition of a prepotent response in the context of three formal models of the limits of WMC: A resources model, a decay-based model, and three versions of the IM. The resources model was built on the assumption that a limited and shared source of activation for the maintenance and manipulation of the objects underlies the limits of WMC. The decay model assumes that memory traces of the working-memory objects decay over time if they are not reactivated via different mechanisms of maintenance. The IM, already described, proposes that interference-related mechanisms explain the limits of WMC. In two experiments and in a reanalysis of data of the second experiment, one version of the IM received more statistical support from the data. This version of the IM proposes that interference by feature overwriting and interference by confusion are the main factors underlying the limits of WMC. In addition, the model suggests that experimental conditions involving the inhibition of a prepotent response reduce the speed of processing and promotes the involuntary activation of irrelevant information in working memory.
Chapter 4 summed up Chapter 2 and 3 and discussed their findings and presented how this thesis has provided evidence of interference-related mechanisms as the main cause of forgetting, and it has attempted to clarify the role of inhibition and attentional control in working memory. With the implementation of formal models and experimental manipulations in the framework of nonlinear mixed models the data offered explanations of causes of forgetting and the role of inhibition in WMC at different levels: developmental effects, aging effects, effects related to experimental manipulations and individual differences in these effects. Thus, the present approach afforded a comprehensive view of a large number of factors limiting WMC.
Various synthetic approaches were explored towards the preparation of poly(N-substituted glycine) homo/co-polymers (a.k.a. polypeptoids). In particular, monomers that would facilitate in the preparation of bio-relevant polymers via either chain- or step-growth polymerization were targeted. A 3-step synthetic approach towards N-substituted glycine N-carboxyanhydrides (NNCA) was implemented, or developed, and optimized allowing for an efficient gram scale preparation of the aforementioned monomer (chain-growth). After exploring several solvents and various conditions, a reproducible and efficient ring-opening polymerization (ROP) of NNCAs was developed in benzonitrile (PhCN). However, achieving molecular weights greater than 7 kDa required longer reaction times (>4 weeks) and sub-sequentially allowed for undesirable competing side reactions to occur (eg. zwitterion monomer mechanisms). A bulk-polymerization strategy provided molecular weights up to 11 kDa within 24 hours but suffered from low monomer conversions (ca. 25%). Likewise, a preliminary study towards alcohol promoted ROP of NNCAs suffered from impurities and a suspected alternative activated monomer mechanism (AAMM) providing poor inclusion of the initiator and leading to multi-modal dispersed polymeric systems. The post-modification of poly(N-allyl glycine) via thiol-ene photo-addition was observed to be quantitative, with the utilization of photo-initiators, and facilitated in the first glyco-peptoid prepared under environmentally benign conditions. Furthermore, poly(N-allyl glycine) demonstrated thermo-responsive behavior and could be prepared as a semi-crystalline bio-relevant polymer from solution (ie. annealing). Initial efforts in preparing these polymers via standard poly-condensation protocols were insufficient (step-growth). However, a thermally induced side-product, diallyl diketopiperazine (DKP), afforded the opportunity to explore photo-induced thiol-ene and acyclic diene metathesis (ADMET) polymerizations. Thiol-ene polymerization readily led to low molecular weight polymers (<2.5 kDa), that were insoluble in most solvents except heated amide solvents (ie. DMF), whereas ADMET polymerization, with diallyl DKP, was unsuccessful due to a suspected 6 member complexation/deactivation state of the catalyst. This understanding prompted the preparation of elongated DKPs most notably dibutenyl DKP. SEC data supports the aforementioned understanding but requires further optimization studies in both the preparation of the DKP monomers and following ADMET polymerization. This work was supported by NMR, GC-MS, FT-IR, SEC-IR, and MALDI-Tof MS characterization. Polymer properties were measured by UV-Vis, TGA, and DSC.
This cumulative dissertation explored the use of the detection of natural background of fast neutrons, the so-called cosmic-ray neutron sensing (CRS) approach to measure field-scale soil moisture in cropped fields. Primary cosmic rays penetrate the top atmosphere and interact with atmospheric particles. Such interaction results on a cascade of high-energy neutrons, which continue traveling through the atmospheric column. Finally, neutrons penetrate the soil surface and a second cascade is produced with the so-called secondary cosmic-ray neutrons (fast neutrons). Partly, fast neutrons are absorbed by hydrogen (soil moisture). Remaining neutrons scatter back to the atmosphere, where its flux is inversely correlated to the soil moisture content, therefore allowing a non-invasive indirect measurement of soil moisture. The CRS methodology is mainly evaluated based on a field study carried out on a farmland in Potsdam (Brandenburg, Germany) along three crop seasons with corn, sunflower and winter rye; a bare soil period; and two winter periods. Also, field monitoring was carried out in the Schaefertal catchment (Harz, Germany) for long-term testing of CRS against ancillary data. In the first experimental site, the CRS method was calibrated and validated using different approaches of soil moisture measurements. In a period with corn, soil moisture measurement at the local scale was performed at near-surface only, and in subsequent periods (sunflower and winter rye) sensors were placed in three depths (5 cm, 20 cm and 40 cm). The direct transfer of CRS calibration parameters between two vegetation periods led to a large overestimation of soil moisture by the CRS. Part of this soil moisture overestimation was attributed to an underestimation of the CRS observation depth during the corn period ( 5-10 cm), which was later recalculated to values between 20-40 cm in other crop periods (sunflower and winter rye). According to results from these monitoring periods with different crops, vegetation played an important role on the CRS measurements. Water contained also in crop biomass, above and below ground, produces important neutron moderation. This effect was accounted for by a simple model for neutron corrections due to vegetation. It followed crop development and reduced overall CRS soil moisture error for periods of sunflower and winter rye. In Potsdam farmland also inversely-estimated soil hydraulic parameters were determined at the field scale, using CRS soil moisture from the sunflower period. A modelling framework coupling HYDRUS-1D and PEST was applied. Subsequently, field-scale soil hydraulic properties were compared against local scale soil properties (modelling and measurements). Successful results were obtained here, despite large difference in support volume. Simple modelling framework emphasizes future research directions with CRS soil moisture to parameterize field scale models. In Schaefertal catchment, CRS measurements were verified using precipitation and evapotranspiration data. At the monthly resolution, CRS soil water storage was well correlated to these two weather variables. Also clearly, water balance could not be closed due to missing information from other compartments such as groundwater, catchment discharge, etc. In the catchment, the snow influence to natural neutrons was also evaluated. As also observed in Potsdam farmland, CRS signal was strongly influenced by snow fall and snow accumulation. A simple strategy to measure snow was presented for Schaefertal case. Concluding remarks of this dissertation showed that (a) the cosmic-ray neutron sensing (CRS) has a strong potential to provide feasible measurement of mean soil moisture at the field scale in cropped fields; (b) CRS soil moisture is strongly influenced by other environmental water pools such as vegetation and snow, therefore these should be considered in analysis; (c) CRS water storage can be used for soil hydrology modelling for determination of soil hydraulic parameters; and (d) CRS approach has strong potential for long term monitoring of soil moisture and for addressing studies of water balance.