Molekulare Struktur mit Abstand - quantitative Interpretation von Puls Elektron-Elektron Doppelresonanzdaten

Pulsed electron-electron double resonance (PELDOR) is a well established method concerning nanometer distance measurements involving two nitroxide spin-labels. In this thesis the applicability of this method to count the number of spins is tested. Furthermore, this work explored the limits, up to which PELDOR data obtained on copper(II)-nitroxide complexes can be quantitatively interpreted. Spin counting provides access to oligomerization studies – monitoring the assembly of homo- or hetero-oligomers from singly labeled compounds. The experimental calibration was performed using model systems, which contain one to four nitroxide radicals. The results show that monomers, dimers, trimers, and tetramers can be distinguished within an error of 5% in the number of spins. Moreover, a detailed analysis of the distance distributions in model complexes revealed that more than one distance can be extracted from complexes bearing several spins, as for example three different distances were resolved in a model tetramer – the other three possible distances being symmetry related. Furthermore, systems exhibiting mixtures of oligomeric states complicate the analysis of the data, because the average number of spin centers contributes nonlinearly to the signal and different relaxation behavior of the oligomers has to be treated explicitly. Experiments solving these problems are proposed in the thesis. Thus, for the first time spin counting has been experimentally calibrated using fully characterized test systems bearing up to four spins. Moreover, the behavior of mixtures was quantitatively interpreted. In addition, it has been shown that several spin-spin distances within a molecule can be extracted from a single dataset. In the second part of the thesis PELDOR experiments on a spin-labeled copper(II)-porphyrin have been quantitatively analyzed. Metal-nitroxide distance measurements are a valuable tool for the triangulation of paramagnetic metal ions. Therefore, X-band PELDOR experiments at different frequencies have been performed. The data exhibits only weak orientation selection, but a fast damping of the oscillation. The experimental data has been interpreted based upon quantitative simulations. The influence of orientation selection, conformational flexibility, spin-density distribution, exchange interaction J, as well as anisotropy and strains of the g-tensor has been examined. An estimate of the spin-density delocalization has been obtained by density functional theory calculations. The dipolar interaction tensor was calculated from the point-charge model, the extension of the point-dipole approximation to several spin bearing centers. Even assuming asymmetric spin distributions induced by an ensemble of asymmetrically distorted porphyrins the effect of delocalization on the PELDOR time trace is weak. The observed damping of dipolar oscillations has been only reproduced by simulations, if a small distribution in J was assumed. It has been shown that the experimental damping of dipolar modulations is not solely due to conformational heterogeneity. In conclusion the quantitative interpretation of PELDOR data is extended to copper-nitroxide- and multi-spin-systems. The influence of the mean distance, of the number of coupled spins, of the conformational flexibility, of spin-density distribution and of the electronic structure of the spin centers has been analyzed using model systems. The insights on model compounds mimicking spin-labeled biomacromolecules – in oligomeric or metal bound states – calibrate the method with respect to the information that can be deduced from the experimental data. The resulting in-depth understanding allows correlating experimental results (from for example biological systems) with models of structure and dynamics. It also opens new fields for PELDOR as for example triangulation of metal centers and oligomerization studies. In general, this thesis has demonstrated that modern pulsed electron paramagnetic resonance techniques in combination with quantitative data analysis can contribute to a detailed insight into molecular structure and dynamics

High-versus Low-Context National Cultures: Preferences for Type of Retailer and for Human Interaction

A purpose of this research is to investigate differences between low-and high-context national cultures in retail settings. In particular, we examined cultural differences in preference for human interaction while shopping, emotional warmth characteristics, perception of quality service, and retail channel preferences. As businesses more frequently employ multi-channel strategies in global settings, this topic of national culture gains importance and can shed light on key factors that shape consumers\u27 retail preferences. Our findings indicate that national cultures differ in terms of retail channel preferences, preference for human interaction, and relationships between the two. Managerial implications and future research are addressed, as well as our study\u27s limitations

In the shadows of a hypergraph: looking for associated primes of powers of square-free monomial ideals

The aim of this paper is to study the associated primes of powers of square-free monomial ideals. Each square-free monomial ideal corresponds uniquely to a finite simple hypergraph via the cover ideal construction, and vice versa. Let H be a finite simple hypergraph and J(H) the cover ideal of H. We define the shadows of hypergraph, H, described as a collection of smaller hypergraphs related to H under some conditions. We then investigate how the shadows of H preserve information about the associated primes of the powers of J(H). Finally, we apply our findings on shadows to study the persistence property of square-free monomial ideals and construct some examples exhibiting failure of containment

Monitoring complex formation by relaxation-induced pulse electron paramagnetic resonance distance measurements

Funding: EPSRC DTC and Wellcome (099149/Z/12/Z).Biomolecular complexes are often multimers fueling the demand for methods that allow unraveling their composition and geometric arrangement. Pulse electron paramagnetic resonance (EPR) spectroscopy is increasingly applied for retrieving geometric information on the nanometer scale. The emerging RIDME (relaxation-induced dipolar modulation enhancement) technique offers improved sensitivity in distance experiments involving metal centers (e.g. on metalloproteins or proteins labelled with metal ions). Here, a mixture of a spin labelled ligand with increasing amounts of paramagnetic CuII ions allowed accurate quantification of ligand-metal binding in the model complex formed. The distance measurement was highly accurate and critical aspects for identifying multimerization could be identified. The potential to quantify binding in addition to the high-precision distance measurement will further increase the scope of EPR applications.Publisher PDFPeer reviewe

Initial data for black hole-neutron star binaries, with rotating stars

The coalescence of a neutron star with a black hole is a primary science target of ground-based gravitational wave detectors. Constraining or measuring the neutron star spin directly from gravitational wave observations requires knowledge of the dependence of the emission properties of these systems on the neutron star spin. This paper lays foundations for this task, by developing a numerical method to construct initial data for black hole--neutron star binaries with arbitrary spin on the neutron star. We demonstrate the robustness of the code by constructing initial-data sets in large regions of the parameter space. In addition to varying the neutron star spin-magnitude and spin-direction, we also explore neutron star compactness, mass-ratio, black hole spin, and black hole spin-direction. Specifically, we are able to construct initial data sets with neutron stars spinning near centrifugal break-up, and with black hole spins as large as $S_{\rm BH}/M_{\rm BH}^2=0.99$.Comment: 25 pages, 12 figure

Massive disk formation in the tidal disruption of a neutron star by a nearly extremal black hole

Black hole-neutron star (BHNS) binaries are important sources of gravitational waves for second-generation interferometers, and BHNS mergers are also a proposed engine for short, hard gamma-ray bursts. The behavior of both the spacetime (and thus the emitted gravitational waves) and the neutron star matter in a BHNS merger depend strongly and nonlinearly on the black hole's spin. While there is a significant possibility that astrophysical black holes could have spins that are nearly extremal (i.e. near the theoretical maximum), to date fully relativistic simulations of BHNS binaries have included black-hole spins only up to $S/M^2$=0.9, which corresponds to the black hole having approximately half as much rotational energy as possible, given the black hole's mass. In this paper, we present a new simulation of a BHNS binary with a mass ratio $q=3$ and black-hole spin $S/M^2$=0.97, the highest simulated to date. We find that the black hole's large spin leads to the most massive accretion disk and the largest tidal tail outflow of any fully relativistic BHNS simulations to date, even exceeding the results implied by extrapolating results from simulations with lower black-hole spin. The disk appears to be remarkably stable. We also find that the high black-hole spin persists until shortly before the time of merger; afterwards, both merger and accretion spin down the black hole.Comment: 20 pages, 10 figures, submitted to Classical and Quantum Gravit