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The distinction of enantiomers is a key aspect of chemical analysis. In mass spectrometry the distinction of enantiomers has been achieved by ionizing the sample with circularly polarized laser pulses and comparing the ion yields for light of opposite handedness. While resonant excitation conditions are expected to be most efficient, they are not required for the detection of a circular dichroism (CD) in the ion yield. However, the prediction of the size and sign of the circular dichroism becomes challenging if non-resonant multiphoton excitations are used to ionize the sample. Employing femtosecond laser pulses to drive electron wavepacket dynamics based on ab initio calculations, we attempt to reveal underlying mechanisms that determine the CD under non-resonant excitation conditions. Simulations were done for (R)-1,2-propylene oxide, using time-dependent configuration interaction singles with perturbative doubles (TD-CIS(D)) and the aug-cc-pVTZ basis set. Interactions between the electric field and the electric dipole and quadrupole as well as between the magnetic field and the magnetic dipole were explicitly accounted for. The ion yield was determined by treating states above the ionization potential as either stationary or non-stationary with energy-dependent lifetimes based on an approved heuristic approach. The observed population dynamics do not allow for a simple interpretation, because of highly non-linear interactions. Still, the various transition pathways are governed by resonant enantiospecific n-photon excitation, with preferably high transition dipole moments, which eventually dominate the CD in the ionized population.
Exposure to organic mercury compounds promotes primarily neurological effects. Although methylmercury is recognized as a potent neurotoxicant, its transfer into the central nervous system (CNS) is not fully evaluated. While methylmercury and thiomersal pass the blood–brain barrier, limited data are available regarding the second brain regulating interface, the blood–cerebrospinal fluid (CSF) barrier. This novel study was designed to investigate the effects of organic as well as inorganic mercury compounds on, and their transfer across, a porcine in vitro model of the blood–CSF barrier for the first time. The barrier system is significantly more sensitive towards organic Hg compounds as compared to inorganic compounds regarding the endpoints cytotoxicity and barrier integrity. Whereas there are low transfer rates from the blood side to the CSF side, our results strongly indicate an active transfer of the organic mercury compounds out of the CSF. These results are the first to demonstrate an efflux of organic mercury compounds regarding the CNS and provide a completely new approach in the understanding of mercury compounds specific transport.
Arsenic-containing fatty acids are a group of fat-soluble arsenic species (arsenolipids) which are present in marine fish and other seafood. Recently, it has been shown that arsenic-containing hydrocarbons, another group of arsenolipids, exert toxicity in similar concentrations comparable to arsenite although the toxic modes of action differ. Hence, a risk assessment of arsenolipids is urgently needed. In this study the cellular toxicity of a saturated (AsFA 362) and an unsaturated (AsFA 388) arsenic-containing fatty acid and three of their proposed metabolites (DMAV, DMAPr and thio-DMAPr) were investigated in human liver cells (HepG2). Even though both arsenic-containing fatty acids were less toxic as compared to arsenic-containing hydrocarbons and arsenite, significant effects were observable at μM concentrations. DMAV causes effects in a similar concentration range and it could be seen that it is metabolised to its highly toxic thio analogue thio-DMAV in HepG2 cells. Nevertheless, DMAPr and thio-DMAPr did not exert any cytotoxicity. In summary, our data indicate that risks to human health related to the presence of arsenic-containing fatty acids in marine food cannot be excluded. This stresses the need for a full in vitro and in vivo toxicological characterisation of these arsenolipids.
The main research question of this thesis concerns the relation between focus interpretation, focus realization, and association with focus in the West Chadic language Ngamo.
Concerning the relation between focus realization and interpretation, this thesis contributes to the question, cross-linguistically, what factors influence a marked realization of the focus/background distinction. There is background-marking rather than focus-marking in Ngamo, and the background marker is related to the definite determiner in the language. Using original fieldwork data as a basis, a formal semantic analysis of the background marker as a definite determiner of situations is proposed.
Concerning the relation between focus and association with focus, the thesis adds to the growing body of crosslinguistic evidence that not all so-called focus-sensitive operators always associate with focus. The thesis shows that while the exclusive particle yak('i) (= "only") in Ngamo conventionally associates
with focus, the particles har('i) (= "even, as far as, until, already"), and ke('e) (= "also, and") do not.
The thesis provides an analysis of these phenomena in a situation semantic framework.
KEYCIT 2014
(2015)
In our rapidly changing world it is increasingly important not only to be an expert in a chosen field of study but also to be able to respond to developments, master new approaches to solving problems, and fulfil changing requirements in the modern world and in the job market. In response to these needs key competencies in understanding, developing and using new digital technologies are being brought into focus in school and university programmes. The IFIP TC3 conference "KEYCIT – Key Competences in Informatics and ICT (KEYCIT 2014)" was held at the University of Potsdam in Germany from July 1st to 4th, 2014 and addressed the combination of key competencies, Informatics and ICT in detail. The conference was organized into strands focusing on secondary education, university education and teacher education (organized by IFIP WGs 3.1 and 3.3) and provided a forum to present and to discuss research, case studies, positions, and national perspectives in this field.
Die fortschreitende Diffusion von E-Government ist ein Phänomen, dem in der internationa-len Forschungsliteratur bereits viel Aufmerksamkeit zu Teil wurde. Erstaunlich wenige Studien widmen sich bislang jedoch dezidiert dem Faktor Interdependenz, der eigentlichen Ursache von Diffusionsprozessen. In dieser Arbeit werden Interdependenzbeziehungen anhand dreier spezifischer Mechanismen der Diffusion, namentlich „Nachahmung“, „Wettbewerb“ und „Lernen“, untersucht. Auf Basis einer empirischen Analyse mit Daten zur Einführung von E-Government-Komponenten in 183 deutschen Städten über den Zeitraum von 1995 bis 2014 konnte ein Einfluss der Mechanismen „Nachahmung“ und „Lernen“ auf das Innovationsverhalten von Kommunen festgestellt werden. Für das Vorliegen von Wettbe-werbsdynamiken ließen sich demgegenüber keine Anhaltspunkte finden. Für zukünftige Forschungen zur Diffusion von Innovationen wird angeregt, verstärkt an die mechanismen- und prozessbasierte Perspektive von Diffusion als theoretischem Rahmenkonzept anzuknüpfen.
Evaluation komplexer Systeme
(2015)
Seit von Foerster können wir soziale Systeme als Black Boxes betrachten, zu deren Funktionsweise keine klaren Wenn-Dann-Aussagen möglich erscheinen und deren Operationsweise sich für den Beobachter immer nur sequenziell und sprunghaft – und folglich nie ganzheitlich – darstellt. Jedes Bemühen, ein soziales System tiefgründig verstehen und abbilden zu wollen, kann somit schnell ein Gefühl von Orientierungslosigkeit und Überforderung auslösen – ähnlich, wie während einer Achterbahnfahrt. Für die Evaluationsdebatte resultiert aus dieser Sichtweise die Kernfrage, wie nun also im Rahmen von Evaluationen mit sozialer Komplexität umgegangen werden kann.
An diese Frage anknüpfend stellt der vorliegende Band das Feld der systemischen Therapie- und Beratungsansätze als inspirierenden Fundus vor, aus welchem sich Konzepte, Methoden und Techniken zur Gestaltung von Evaluationsvorhaben ableiten lassen. Aber welche Möglichkeiten und Grenzen offenbaren sich dabei? Lässt sich sozialer Komplexität mit Hilfe dieser Ansätze besser begegnen? Welche Rahmenbedingungen sollten dabei erfüllt sein und wie lassen sich systemische von nicht-systemischen Ansätzen unterscheiden?
In this thesis we utilize resolved stellar populations to improve our understanding of galaxy formation and evolution. In the first part we improve a method for metallicity determination of faint old stellar systems, in the second and third part we analyze the individual history of six nearby disk galaxies outside the Local Group.
A New Calibration of the Color Metallicity Relation of Red Giants for HST data:
It is well known, that the color distribution of stars on the the Red Giant Branch (RGB) can be used to determine metallicities of old stellar populations that have only shallow photometry. Based on the largest sample of globular clusters ever used for such studies, we quantify the relation between metallicity and color in the widely used HST ACS filters F606W and F814W.
We use a sample of globular clusters from the ACS Globular Cluster Survey and measure their RGB color at given absolute magnitudes to derive the color-metallicity relation. We find a clear relation between metallicity and RGB color; we investigate the scatter and the uncertainties in this relation and show its limitations. A comparison with isochrones shows reasonably good agreement with BaSTI models, a small offset to Dartmouth models, and a larger offset to Padua models.
Even for the best globular cluster data available, the metallicity of a simple stellar population can be determined from the RGB alone only with an accuracy of 0.3 dex for [M/H]<-1, and 0.15 dex for [M/H]>-1. For mixed populations, as they are observed in external galaxies, the uncertainties will be even larger due to uncertainties in extinction, age, etc. Therefore caution is necessary when interpreting photometric metallicities.
The Structural History of Nearby Low Mass Disk Galaxies:
We study the individual evolution histories of three nearby, low-mass, edge-on galaxies (IC5052, NGC4244, NGC5023).
Using the color magnitude diagrams of resolved stellar populations, we construct star count density maps for populations of different ages and analyze the change of structural parameters with stellar age within each galaxy.
The three galaxies show low vertical heating rates, which are much lower than the heating rate of the Milky Way. This indicates that heating agents, as giant molecular clouds and spiral structure are weak in low mass galaxies.
We do not detect a separate thick disk in any of the three galaxies, even though our observations cover a larger range in equivalent surface brightness than any integrated light study. While scaleheights increase with age, each population can be well described by a single disk. Only two of the galaxies contain a very weak additional component, which we identify as the faint halo. The mass of these faint halos is less than 1% of the mass of the disk.
All populations in the three galaxies exhibit no or only little flaring. While this finding is consistent with previous integrated light studies, it poses strong constraints on galaxy formation models, because most theoretical simulations often find strong flaring due to interactions or radial migration.
Furthermore, we find breaks in the radial profiles of all three galaxies. The radii of these breaks are independent of age, and the break strength is decreasing with age in two of the galaxies (NGC4244 and NGC5023). This is consistent with break formation models, that combine a star formation cutoff with radial migration. The differing behavior of IC5052 can be explained by a recent interaction or minor merger.
The Structural History of Massive Disk Galaxies:
We extend the structural analysis of stellar populations with distinct ages to three massive galaxies, NGC891, NGC4565 and NGC7814. While confusion effects due to the high stellar number densities in their central region, and the prominent dust lanes inhibit an detailed analysis of the radial profiles, we can study their vertical structure.
These massive galaxies also have a slower heating than the Milky Way, comparable to the low mass galaxies. This can be traced back to their already thick young populations and thick layers of their interstellar medium.
We do not find a clear separate thick disk in any of these three galaxies; all populations can be described by a single disk plus a S\'ersic bulge/halo component. In contrast to the low mass galaxies, we cannot rule out the presence of thick disks in the massive galaxies, because of the strong influence of the halo, that might hide the possible contribution of the thick disk to the vertical star count profiles. However, the faintness of the possible thick disks still points to problems in the earlier ubiquitous findings of thick disks in external galaxies.
Die Honigbiene Apis mellifera zeigt innerhalb einer Kolonie eine an das Alter gekoppelte Arbeitsteilung. Junge Honigbienen versorgen die Brut (Ammenbienen), während ältere Honigbienen (Sammlerinnen) außerhalb des Stocks Pollen und Nektar eintragen. Die biogenen Amine Octopamin und Tyramin sind an der Steuerung der Arbeitsteilung maßgeblich beteiligt. Sie interagieren mit Zielzellen über die Bindung an G Protein gekoppelte Rezeptoren. A. mellifera besitzt fünf charakterisierte Octopaminrezeptoren (AmOctαR1, AmOctβR1-4), einen charakterisierten Tyraminrezeptor (AmTyr1) sowie einen weiteren putativen Tyraminrezeptor.
In der vorliegenden Arbeit wurde dieser putative Aminrezeptor als zweiter Tyraminrezeptor (AmTyr2) identifiziert, lokalisiert und pharmakologisch charakterisiert.
Die von der cDNA abgeleitete Aminosäuresequenz weist strukturelle Eigenschaften und konservierte Motive von G Protein gekoppelten Rezeptoren auf. Phylogenetisch ordnet sich der AmTyr2 Rezeptor bei den Tyramin 2 Rezeptoren anderer Insekten ein. Die funktionelle und pharmakologische Charakterisierung des putativen Tyraminrezeptors erfolgte in modifizierten HEK293 Zellen, die mit der Rezeptor cDNA transfiziert wurden. Die Applikation von Tyramin aktiviert Adenylylcyclasen in diesen Zellen und resultiert in einem Anstieg des intrazellulären cAMP Gehalts. Der AmTyr2 Rezeptor kann durch Tyramin in nanomolaren Konzentrationen halbmaximal aktiviert werden. Während es sich bei Octopamin um einen wirkungsvollen Agonisten des Rezeptors handelt, sind Mianserin und Yohimbin effektive Antagonisten. Für die Lokalisierung des Rezeptorproteins wurde ein polyklonaler Antikörper generiert. Eine AmTyr2-ähnliche Immunreaktivität zeigt sich im Gehirn in den optischen Loben, den Antennalloben, dem Zentralkomplex und in den Kenyon Zellen der Pilzkörper.
Des Weiteren wurde die Rolle der Octopamin- und Tyraminrezeptoren bei der Steuerung der altersabhängigen Arbeitsteilung analysiert.
Die Genexpression des AmOctαR1 in verschiedenen Gehirnteilen korreliert unabhängig vom Alter mit der sozialen Rolle, während sich die Genexpression von AmOctβR3/4 und den Tyraminrezeptoren AmTyr1 und AmTyr2 maximal mit dem Alter aber nicht der sozialen Rolle ändert. Sammlerinnen weisen einen höheren Octopamingehalt im Gesamtgehirn auf als Ammenbienen; bei Tyramin zeigen sich keine Unterschiede. Während Tyramin offensichtlich keine direkte Rolle spielt, werden durch Octopamin gesteuerte Prozesse der altersabhängigen Arbeitsteilung bei der Honigbiene vermutlich über den AmOctαR1 vermittelt.
Die Ergebnisse der vorliegenden Arbeit zeigen die wichtige Rolle von biogenen Aminen, insbesondere Octopamin bei der sozialen Organisation von Insektenstaaten.