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This thesis presents research studies on the fundamental interplay of diatomic molecules with transition metal compounds under cryogenic conditions. The utilized setup offers a multitude of opportunities to study isolated ions: The ions can either be generated by an ElectroSpray Ionization (ESI) source or a Laser VAPorization (LVAP) cluster ion source. The setup facilitates kinetic investigations of the ions with different reaction gases under well-defined isothermal conditions. Moreover it enables cryo InfraRed (Multiple) Photon Dissociation (IR-(M)PD) spectroscopy in combination with tunable OPO/OPA laser systems. In conjunction with density functional theory (DFT) modelling, the IR(M)-PD spectra allow for an assignment of geometric minimum structures. Furthermore DFT modelling helps to identify possible reaction pathways. Altogether the presented methods allow to gain fundamental insights into molecular structures and reactivity of the investigated systems.
The first part of this thesis focuses on the interplay of N2 with different transition metal clusters (Con+, Nin+, and Fen+) by cryo IR spectroscopy and cryo kinetics. In conjunction with DFT modelling the N2 coordination was elucidated (Con+), structures were assigned (Nin+), the concept of structure related surface adsorption behavior was introduced (Nin+), and the a first explanation for the inertness if Fe17+ was given (Fen+). Furthermore this thesis provides for a case study on the coadsorption of H2 and N2 on Ru8+ that elucidates the H migration on the Ru cluster. The last part of the thesis addresses the IR spectra of in vacuo generated [Hemin]+ complexes with N2, O2, and CO. Structures and spin states were assigned with the help of DFT modelling.
This thesis comprises investigations on the interaction of \(N_2\) adsorbate molecules with size-selected iron metal clusters under cryo conditions. All investigations were performed at the customized fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer FRITZ. This setup serves a laser vaporization (LVAP) source to generate the investigated iron cluster ions. Cryo kinetic studies investigate the stepwise \(N_2\) adsorption on size selected \(Fe_n^+\) clusters under well-defined isothermal conditions. The adsorption behavior and the adsorption limits lead to information about the cluster structure and its reactivity. By coupling a tunable IR laser in the ICR cell, it is possible to perform cryo infrared photon dissociation (IR-PD) spectroscopy experiments. This provides information on binding motifs of the \(N_2\) adsorbates and the cluster structure. Combining both methods with quantum chemical calculations via density functional theory (DFT) substantiates the experimental results and deepens the fundamental insights into the cluster structure, their reactivity, and the metal-adsorbate bonding.
Prostate cancer preferentially metastasizes to the skeleton and abundant evidence exists that osteoblasts specifically support the metastatic process, including cancer stem cell niche formation. At early stages of bone metastasis, crosstalk of prostate cancer cells and osteoblasts through soluble molecules results in a decrease of cancer cell proliferation, accompanied by altered adhesive properties and increased expression of bone-specific genes, or osteomimicry. Osteoblasts synthesize a plethora of biologically active factors, which comprise the unique bone microenvironment. By means of quantitative real-time RT-PCR it was determined that exposure to the osteoblast secretome induced gene expression changes in prostate cancer cells, including the upregulation of osteomimetic genes such as BMP2, AP, COL1A1, OPG and RANKL. IL6 and TGFbeta1 signaling pathway components also became upregulated at early time points. Moreover, osteoblast-released IL6 and TGFbeta1 contributed to the upregulation of OPG mRNA in LNCaP. Thus, the earliest response of prostate cancer cells to osteoblast-released factors, which ultimately cause metastatic cells to assume an osteomimetic phenotype, involved activation of paracrine and autocrine IL6 and TGFbeta signaling. On the other hand, a microarray analysis showed that osteoblasts exposed to the secretome of prostate cancer cells exhibited gene expression alterations suggestive of repressed proliferation, decreased matrix synthesis and inhibited immune response, which together indicate enhanced preosteocytic differentiation. TGFbeta signaling, known to inhibit osteoblast maturation, was strongly suppressed, as shown by elevated expression of negative regulators, downregulation of pathway components and of numerous target genes. Transcriptional downregulation of osteoblast inhibitory molecules such as DKK1 and FST also occurred, with concomitant upregulation of the osteoinductive molecules ADM, STC1 and BMP2, and of the transcription factors CBFA1 and HES1, which promote osteoblast differentiation. Finally, the mRNA encoding NPPB, the precursor of a molecule implicated in the inhibition of TGFbetaeffects, in bone formation and in stem cell maintenance, became upregulated after coculture both in osteoblasts and in prostate cancer cells. These results provide an insight into potential mechanisms of dysregulated bone formation in metastatic prostate cancer, as well as mechanisms by which osteoblasts might enhance the invasive, osteomimetic and stem cell-like properties of the tumor cells. In particular, the differential modulation of TGFbetasignaling in prostate cancer cells and osteoblasts appears to merit further research.
In this study we investigated parafoveal processing by L1 and late L2 speakers of English (L1 German) while reading in English.
We hypothesized that L2ers would make use of semantic and orthographic information parafoveally. Using the gaze contingent
boundary paradigm, we manipulated six parafoveal masks in a sentence (Mark found th*e wood for the fire; * indicates the
invisible boundary): identical word mask (wood), English orthographic mask (wook), English stringmask (zwwl), German mask
(holz), German orthographic mask (holn), and German string mask (kxfs). We found an orthographic benefit for L1ers and L2ers
when the mask was orthographically related to the target word (wood vs. wook) in line with previous L1 research. English L2ers
did not derive a benefit (rather an interference) when a non-cognate translation mask from their L1 was used (wood vs. holz), but
did derive a benefit from a German orthographic mask (wood vs. holn). While unexpected, it may be that L2ers incur a switching
cost when the complete German word is presented parafoveally, and derive a benefit by keeping both lexicons active when a
partial German word is presented parafoveally (narrowing down lexical candidates). To the authors’ knowledge there is no
mention of parafoveal processing in any model of L2 processing/reading, and the current study provides the first evidence for a
parafoveal non-cognate orthographic benefit (but only with partial orthographic overlap) in sentence reading for L2ers. We
discuss how these findings fit into the framework of bilingual word recognition theories.
Abstract: The classification of quasi - primary fields is outlined. It is proved that the only conserved quasi - primary currents are the energy - momentum tensor and the O(N)-Noether currents. Derivation of all quasi - primary fields and the resolution of degeneracy is sketched. Finally the limits d = 2 and d = 4 of the space dimension are discussed. Whereas the latter is trivial the former is only almost so. (To appear in the Proceedings of the XXII Conference on Differential Geometry Methods in Theoretical Physics, Ixtapa, Mexico, September 20-24, 1993)
Leisen, Thomas ; Bietz, Fabian ; Werner, Janina ; Wagner, Alex ; Schaffrath, Ulrich ; Scheuring, David ; Willmund, Felix ; Mosbach, Andreas ; Scalliet, Gabriel ; Hahn, Matthias
CRISPR/Cas has become the state-of-the-art technology for genetic manipulation in diverse
organisms, enabling targeted genetic changes to be performed with unprecedented efficiency. Here we report on the first establishment of robust CRISPR/Cas editing in the important necrotrophic plant pathogen Botrytis cinerea based on the introduction of optimized
Cas9-sgRNA ribonucleoprotein complexes (RNPs) into protoplasts. Editing yields were further improved by development of a novel strategy that combines RNP delivery with cotransformation of transiently stable vectors containing telomeres, which allowed temporary
selection and convenient screening for marker-free editing events. We demonstrate that
this approach provides superior editing rates compared to existing CRISPR/Cas-based
methods in filamentous fungi, including the model plant pathogen Magnaporthe oryzae.
Genome sequencing of edited strains revealed very few additional mutations and no evidence for RNP-mediated off-targeting. The high performance of telomere vector-mediated
editing was demonstrated by random mutagenesis of codon 272 of the sdhB gene, a major
determinant of resistance to succinate dehydrogenase inhibitor (SDHI) fungicides by in bulk
replacement of the codon 272 with codons encoding all 20 amino acids. All exchanges were
found at similar frequencies in the absence of selection but SDHI selection allowed the identification of novel amino acid substitutions which conferred differential resistance levels
towards different SDHI fungicides. The increased efficiency and easy handling of RNPbased cotransformation is expected to accelerate molecular research in B. cinerea and
other fungi.
The present work investigated three important constructs in the field of psychology: creativity, intelligence and giftedness. The major objective was to clarify some aspects about each one of these three constructs, as well as some possible correlations between them. Of special interest were: (1) the relationship between creativity and intelligence - particularly the validity of the threshold theory; (2) the development of these constructs within average and above-average intelligent children and throughout grade levels; and (3) the comparison between the development of intelligence and creativity in above-average intelligent primary school children that participated in a special program for children classified as “gifted”, called Entdeckertag (ET), against an age-class- and-IQ matched control group. The ET is a pilot program which was implemented in 2004 by the Ministry for Education, Science, Youth and Culture of the state of Rhineland-Palatinate, Germany. The central goals of this program are the early recognition of gifted children and intervention, based on the areas of German language, general science and mathematics, and also to foster the development of a child’s creativity, social ability, and more. Five hypotheses were proposed and analyzed, and reported separately within five chapters. To analyze these hypotheses, a sample of 217 children recruited from first to fourth grade, and between the ages of six and ten years, was tested for intelligence and creativity. Children performed three tests: Standard Progressive Matrices (SPM) for the assessment of classical intelligence, Test of Creative Thinking – Drawing Production (TCT-DP) for the measurement of classical creativity, and Creative Reasoning Task (CRT) for the evaluation of convergent and divergent thinking, both in open problem spaces. Participants were divided according to two general cohorts: Intervention group (N = 43), composed of children participating in the Entdeckertag program, and a non-intervention group (N = 174), composed of children from the regular primary school. For the testing of the hypotheses, children were placed into more specific groups according to the particular hypothesis that was being tested. It could be concluded that creativity and intelligence were not significantly related and the threshold theory was not confirmed. Additionally, intelligence accounted for less than 1% of the variance within creativity; moreover, scores on intelligence were unable to predict later creativity scores. The development of classical intelligence and classical creativity throughout grade levels also presented a different pattern; intelligence grew increasingly and continually, whereas creativity stagnated after the third grade. Finally, the ET program proved to be beneficial for classical intelligence after two years of attendance, but no effect was found for creativity. Overall, results indicate that organizations and institutions such as schools should not look solely to intelligence performance, especially when aiming to identify and foster gifted or creative individuals.
In tribology laboratories, the management of material samples and test specimens, the planning and execution of experiments, the evaluation of test data and the longterm storage of results are critical processes. However, despite their criticality, they are carried out manually and typically at a low level of computerization and standardization. Therefore, formats for primary data and aggregated results are wildly different between laboratories, and the interoperability of research data is low. Even within laboratories, low levels of standardization, in combination with ambiguous or non-unique identifiers for data files, test specimens and analysis results greatly reduce data integrity and quality. As a consequence, productivity is low, error rates are high, and the lack or low quality of metadata causes the value of produced data to deteriorate very quickly, which makes the re-use of data, e.g. for data mining and meta studies, practically impossible.
In other fields of science, these are mitigated by the use of Laboratory Information Management Systems (LIMS). However, at the moment, such systems do not exist
in tribological research. The main challenge for the implementation of such a system is that it requires extensive interdisciplinary knowledge from otherwise very
disparate fields: tribology, data and process modelling, quality management, databases and programming. So far, existing solutions are either proprietary, very limited
in their scope or focused on merely storing aggregated results without any support for laboratory operations.
Therefore, this thesis describes fundamentals of information technology, data modelling and programming that are required to build a LIMS for tribology laboratories.
Based on an analysis of a typical workflow of a tribology laboratory, a data model for all relevant entities and processes is designed using object-relational data modelling and object-oriented programming and a relational database is used to provide a reference implementation of such a LIMS. It provides critical functionalities
like a materials database, test specimen management, the planning, execution and evaluation of friction and wear tests, automated procedures for tribometer
parameterization and data transmission, storage and evaluation and for aggregating individual tests into test sets and projects. It improves the quality and long-term usability of data by replacing error-prone human processes by automated variants, e.g. automated collection of metadata and data file transmission, homogenization and storage. The usefulness of the developed LIMS is demonstrated by applying it to Transfer Film Luminance Analysis (TLA), which is a newly developed advanced method for the analysis of the formation and stability of transfer films and their impact on friction and wear, but which produces so much data and requires such a large amount of metadata during evaluation that it can only be performed safely, quickly and reliably by integration into the presented LIMS.
Self-adaptation allows software systems to autonomously adjust their behavior during run-time by handling all possible
operating states that violate the requirements of the managed system. This requires an adaptation engine that receives adaptation
requests during the monitoring process of the managed system and responds with an automated and appropriate adaptation
response. During the last decade, several engineering methods have been introduced to enable self-adaptation in software systems.
However, these methods lack addressing (1) run-time uncertainty that hinders the adaptation process and (2) the performance
impacts resulted from the complexity and the large number of the adaptation space. This paper presents CRATER, a framework
that builds an external adaptation engine for self-adaptive software systems. The adaptation engine, which is built on Case-based
Reasoning, handles the aforementioned challenges together. This paper is braced with an experiment illustrating the benefits of
this framework. The experimental results shows the potential of CRATER in terms handling run-time uncertainty and adaptation
remembrance that enhances the performance for large number of adaptation space.
In traditional portfolio optimization under the threat of a crash the investment horizon or time to maturity is neglected. Developing the so-called crash hedging strategies (which are portfolio strategies which make an investor indifferent to the occurrence of an uncertain (down) jumps of the price of the risky asset) the time to maturity turns out to be essential. The crash hedging strategies are derived as solutions of non-linear differential equations which itself are consequences of an equilibrium strategy. Hereby the situation of changing market coefficients after a possible crash is considered for the case of logarithmic utility as well as for the case of general utility functions. A benefit-cost analysis of the crash hedging strategy is done as well as a comparison of the crash hedging strategy with the optimal portfolio strategies given in traditional crash models. Moreover, it will be shown that the crash hedging strategies optimize the worst-case bound for the expected utility from final wealth subject to some restrictions. Another application is to model crash hedging strategies in situations where both the number and the height of the crash are uncertain but bounded. Taking the additional information of the probability of a possible crash happening into account leads to the development of the q-quantile crash hedging strategy.