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

Conceptual design study of a Harrier V/STOL research aircraft

MCAIR recently completed a conceptual design study to define modification approaches to, and derive planning prices for the conversion of a two place Harrier to a V/STOL control, display and guidance research aircraft. Control concepts such as rate damping, attitude stabilization, velocity command, and cockpit controllers are to be demonstrated. Display formats will also be investigated, and landing, navigation and guidance systems flight tested. The rear cockpit is modified such that it can be quickly adapted to faithfully simulate the controls, displays and handling qualities of a Type A or Type B V/STOL. The safety pilot always has take command capability. The modifications studied fall into two categories: basic modifications and optional modifications. Technical descriptions of the basic modifications and of the optional modifications are presented. The modification plan and schedule as well as the test plan and schedule are presented. The failure mode and effects analysis, aircraft performance, aircraft weight, and aircraft support are discussed

Improving Performance of Iterative Methods by Lossy Checkponting

Iterative methods are commonly used approaches to solve large, sparse linear systems, which are fundamental operations for many modern scientific simulations. When the large-scale iterative methods are running with a large number of ranks in parallel, they have to checkpoint the dynamic variables periodically in case of unavoidable fail-stop errors, requiring fast I/O systems and large storage space. To this end, significantly reducing the checkpointing overhead is critical to improving the overall performance of iterative methods. Our contribution is fourfold. (1) We propose a novel lossy checkpointing scheme that can significantly improve the checkpointing performance of iterative methods by leveraging lossy compressors. (2) We formulate a lossy checkpointing performance model and derive theoretically an upper bound for the extra number of iterations caused by the distortion of data in lossy checkpoints, in order to guarantee the performance improvement under the lossy checkpointing scheme. (3) We analyze the impact of lossy checkpointing (i.e., extra number of iterations caused by lossy checkpointing files) for multiple types of iterative methods. (4)We evaluate the lossy checkpointing scheme with optimal checkpointing intervals on a high-performance computing environment with 2,048 cores, using a well-known scientific computation package PETSc and a state-of-the-art checkpoint/restart toolkit. Experiments show that our optimized lossy checkpointing scheme can significantly reduce the fault tolerance overhead for iterative methods by 23%~70% compared with traditional checkpointing and 20%~58% compared with lossless-compressed checkpointing, in the presence of system failures.Comment: 14 pages, 10 figures, HPDC'1

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

The symbiotic star CH Cygni. III. A precessing radio jet

VLA, MERLIN and Hubble Space Telescope imaging observations of the extended regions of the symbiotic system CH Cygni are analysed. These extensions are evidence of a strong collimation mechanism, probably an accretion disk surrounding the hot component of the system. Over 16 years (between 1985 and 2001) the general trend is that these jets are seen to precess. Fitting a simple ballistic model of matter ejection to the geometry of the extended regions suggests a period of 6520 +/- 150 days, with a precession cone opening angle of 35 +/- 1 degrees. This period is of the same order as that proposed for the orbital period of the outer giant in the system, suggesting a possible link between the two. Anomalous knots in the emission, not explained by the simple model, are believed to be the result of older, slower moving ejecta, or possibly jet material that has become disrupted through sideways interaction with the surrounding medium.Comment: 9 pages, 4 figure

Optimal placement of a limited number of observations for period searches

Robotic telescopes present the opportunity for the sparse temporal placement of observations when period searching. We address the best way to place a limited number of observations to cover the dynamic range of frequencies required by an observer. We show that an observation distribution geometrically spaced in time can minimise aliasing effects arising from sparse sampling, substantially improving signal detection quality. The base of the geometric series is however a critical factor in the overall success of this strategy. Further, we show that for such an optimal distribution observations may be reordered, as long as the distribution of spacings is preserved, with almost no loss of quality. This implies that optimal observing strategies can retain significant flexibility in the face of scheduling constraints, by providing scope for on-the-fly adaptation. Finally, we present optimal geometric samplings for a wide range of common observing scenarios, with an emphasis on practical application by the observer at the telescope. Such a sampling represents the best practical empirical solution to the undersampling problem that we are aware of. The technique has applications to robotic telescope and satellite observing strategies, where target acquisition overheads mean that a greater total target exposure time (and hence signal-to-noise) can often in practice be achieved by limiting the number of observations.Comment: 8 pages with 16 figure

Hubble Space Telescope Imaging of the Expanding Nebular Remnant of the Recurrent Nova RS Ophiuchi (2006)

We report Hubble Space Telescope imaging obtained 155 days after the 2006 outburst of RS Ophiuchi. We detect extended emission in both [O III] and [Ne V] lines. In both lines, the remnant has a double ring structure. The E-W orientation and total extent of these structures (580+-50 AU at d=1.6kpc) is consistent with that expected due to expansion of emitting regions imaged earlier in the outburst at radio wavelengths. Expansion at high velocity appears to have been roughly constant in the E-W direction (v_{exp} = 3200+-300 km/s in the plane of the sky), with tentative evidence of deceleration N-S. We present a bipolar model of the remnant whose inclination is consistent with that of the central binary. The true expansion velocities of the polar components are then v = 5600+-1100 km/s. We suggest that the bipolar morphology of the remnant results from interaction of the outburst ejecta with a circumstellar medium that is significantly denser in the equatorial regions of the binary than at the poles. This is also consistent with observations of shock evolution in the X-ray and the possible presence of dust in the infrared. Furthermore, it is in line with models of the shaping of planetary nebulae with close binary central systems, and also with recent observations relating to the progenitors of Type Ia supernovae, for which recurrent novae are a proposed candidate. Our observations also reveal more extended structures to the S and E of the remnant whose possible origin is briefly discussed.Comment: 13 pages, 2 figures, accepted for publication in ApJ