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Synchrotron-based angle-resolved time-of-flight electron spectroscopy for dynamics in dichalogenides
(2018)
In this thesis, we discuss the characterization of orthogroups by so-called disjunctions of identities. The orthogroups are a subclass of the class of completely regular semigroups, a generalization of the concept of a group. Thus there is for all elements of an orthogroup some kind of an inverse element such that both elements commute. Based on a fundamental result by A.H. Clifford, every completely regular semigroup is a semilattice of completely simple semigroups. This allows the description the gross structure of such semigroup. In particular every orthogroup is a semilattice of rectangular groups which are isomorphic to direct products of rectangular bands and groups. Semilattices of rectangular groups coming from various classes are characterized using the concept of an alternative variety, a generalization of the classical idea of a variety by Birkhoff.
After starting with some fundamental definitions and results concerning semigroups, we introduce the concept of disjunctions of identities and summarize some necessary properties. In particular we present some disjunction of identities which is sufficient for a semigroup for being completely regular. Furthermore we derive from this identity some statements concerning Rees matrix semigroups, a possible representation of completely simple semigroups. A main result of this thesis is the general description of disjunctions of identities such that a completely regular semigroup satisfying the described identity is a semilattice of left groups (right groups / groups). In this case the completely regular semigroup is an orthogroup. Furthermore we define various classes of rectangular groups such that there is an exponent taken from a set of pairwise coprime positive integers. An important result is the characterization of the class of all semilattices of particular rectangular groups (taken from the classes defined before) using a set-theoretic minimal set of disjunctions of identities. Additionally we investigate semilattices of groups (so-called Clifford semigroups). For this purpose we consider abelian groups of particular exponents and prove some well-known results from the theory of Clifford semigroups in an alternative way applying the concept of disjunctions of identities. As a practical application of the results concerning semilattices of left zero semigroups and right zero semigroups we identify a particular transformation semigroup. For more detailed information about the product of two arbitrary elements of a semilattice of semigroups we introduce the concept of strong semilattices of semigroups. It is well-known that a semilattice of groups is a strong semilattice of groups. So we can characterize a strong semilattice of groups of particular pairwise coprime exponents by disjunctions of identities. Additionally we describe the class of all strong semilattices of left zero semigroups and right zero semigroups with the help of such kind of identity, and we relate this statement to the theory of normal bands. A possible extension of the already described semilattices of rectangular groups can be achieved by an auxiliary total order (in terms of chains of semigroups). To this end we present a corresponding characterization due to disjunctions of identities which is obviously minimal. A list of open questions which have arisen during the research for this thesis, but left crude, is attached.
Systemic inflammation is a hallmark of cancer cachexia. Among tumor-host interactions, the white adipose tissue (WAT) is an important contributor to inflammation as it suffers morphological reorganization and lipolysis, releasing free fatty acids (FA), bioactive lipid mediators (LM) and pro-inflammatory cytokines, which accentuate the activation of pro-inflammatory signaling pathways and the recruitment of immune cells to the tissue. This project aimed to investigate which inflammatory factors are involved in the local adipose tissue inflammation and what is the influence of such factors upon enzymes involved in FA or LM metabolism in healthy individuals (Control), weight stable gastro-intestinal cancer patients (WSC) and cachectic cancer patients (CC). The results demonstrated that the inflammatory signature of systemic inflammation is different from local adipose tissue inflammation. The systemic inflammation of the cachectic cancer patients was characterized by higher levels of circulating saturated fatty acids (SFA), tumor-necrosis-factor-α (TNF-α), interleukins IL-6, IL-8 and CRP while levels of polyunsaturated fatty acids (PUFAs), especially n3-PUFAs, were lower in CC than in the other groups. In vitro and in adipose tissue explants, pro-inflammatory cytokines and SFAs were shown to increase the chemokines IL-8 and CXCL10 that were found to be augmented in adipose tissue inflammation in CC which was more profound in the visceral adipose tissue (VAT) than in subcutaneous adipose tissue (SAT). Systemic inflammation was negatively associated with the expression of PUFA synthesizing enzymes, though gene and protein expression did hardly differ between groups. The effects of inflammatory factors on enzymes in the whole tissue could have been masked by differentiated modulation of the diverse cell types in the same tissue. In vitro experiments showed that the expression of FA-modifying enzymes such as desaturases and elongases in adipocytes and macrophages was regulated into opposing directions by TNF-α, IL-6, LPS or palmitate. The higher plasma concentration of the pro-resolving LM resolvin D1 in CC cannot compensate the overall inflammatory status and the results indicate that inflammatory cytokines interfere with synthesis pathways of pro-resolving LM. In summary, the data revealed a complex inter-tissue and inter-cellular crosstalk mediated by pro-inflammatory cytokines and lipid compounds enhancing inflammation in cancer cachexia by feed-forward mechanisms.
Spectroscopy at the limit
(2018)
Neuroinflammatory and neurodegenerative diseases such as Parkinson's (PD) and multiple sclerosis (MS) often result in a severe impairment of the patient´s quality of life. Effective therapies for the treatment are currently not available, which results in a high socio-economic burden. Due to the heterogeneity of the disease subtypes, stratification is particularly difficult in the early phase of the disease and is mainly based on clinical parameters such as neurophysiological tests and central nervous imaging. Due to good accessibility and stability, blood and cerebrospinal fluid metabolite markers could serve as surrogates for neurodegenerative processes. This can lead to an improved mechanistic understanding of these diseases and further be used as "treatment response" biomarkers in preclinical and clinical development programs. Therefore, plasma and CSF metabolite profiles will be identified that allow differentiation of PD from healthy controls, association of PD with dementia (PDD) and differentiation of PD subtypes such as akinetic rigid and tremor dominant PD patients. In addition, plasma metabolites for the diagnosis of primary progressive MS (PPMS) should be investigated and tested for their specificity to relapsing-remitting MS (RRMS) and their development during PPMS progression.
By applying untargeted high-resolution metabolomics of PD patient samples and in using random forest and partial least square machine learning algorithms, this study identified 20 plasma metabolites and 14 CSF metabolite biomarkers. These differentiate against healthy individuals with an AUC of 0.8 and 0.9 in PD, respectively. We also identify ten PDD specific serum metabolites, which differentiate against healthy individuals and PD patients without dementia with an AUC of 1.0, respectively. Furthermore, 23 akinetic-rigid specific plasma markers were identified, which differentiate against tremor-dominant PD patients with an AUC of 0.94 and against healthy individuals with an AUC of 0.98. These findings also suggest more severe disease pathology in the akinetic-rigid PD than in tremor dominant PD. In the analysis of MS patient samples a partial least square analysis yielded predictive models for the classification of PPMS and resulted in 20 PPMS specific metabolites. In another MS study unknown changes in human metabolism were identified after administration of the multiple sclerosis drug dimethylfumarate, which is used for the treatment of RRMS. These results allow to describe and understand the hitherto completely unknown mechanism of action of this new drug and to use these findings for the further development of new drugs and targets against RRMS.
In conclusion, these results have the potential for improved diagnosis of these diseases and improvement of mechanistic understandings, as multiple deregulated pathways were identified. Moreover, novel Dimethylfumarate targets can be used to aid drug development and treatment efficiency. Overall, metabolite profiling in combination with machine learning identified as a promising approach for biomarker discovery and mode of action elucidation.
The topic of this thesis is the experimental investigation of evaporating thin films on planar solid substrates and the enrichment, the crystal growth and Marangoni flows near the three phase line in the case of partially wetting mixtures of volatile and non volatile liquids. In short, it deals with the properties of planar liquid films and with those of thin liquid sections near the three phase contact line. In both cases the liquid looses continuously one component by evaporation. One topic is the rupture behavior of ultra-thin films of binary mixtures of a volatile solvent and a nonvolatile solute. It is studied how the thickness at which the film ruptures is related to the solute crystallization at the liquid/ substrate interface as soon as the solute reaches supersaturation. A universal relation between the rupture thickness and the saturation behaviour is presented. The second research subject are individual nanoparticles embedded in molecularly thin films at planar substrates. It is found that the nanoparticles cause an unexpectedly large film surface distortion (meniscus). This distortion can be measured quantitatively by conventional reflective microscopy although the nanoparticles are much smaller than the Rayleigh diffraction limit. Investigations with binary mixtures of volatile solvents and non-volatile solutes (polymers) aim at a better understanding/prediction of the final solute coverage, the timeresolved film thinning, the time-resolved solvent evaporation, and the evolution of the solute concentration within the thinning film. A quantiative theoretical description of the experimental findings is derived. Experiments of completely miscible binary mixtures of volatile liquids, which individually form continuous planar films show unexpectedly that films of mixtures are not necessarily continuous and planar. Rather, they may form surface
undulations or even rupture. This is explained with surface Marangoni flows. A new method for the exceptionally fast fabrication (mm/min) of ultralong aligned diphenylalanin single crystals via dip casting is presented. It is shown how the specific evaporation conditions at the three phase line can be used for a controlled peptide crystal growth process. It is further demonstrated how the confinement inside a smalll capillary affects the peptide crystallization and how this can be understood (and used).