Structure of Ionic Liquid-Benzene Mixtures

Neutron diffraction has been used to investigate the structure of liquid mixtures of 1,3-dimethylimidazolium hexafluorophosphate with benzene. Two concentrations of benzene were investigated, namely, 33 mol % and 67 mol %, and show similar structures in each case. The presence of benzene significantly alters the ionic liquid structure, in particular, in the cation-cation interactions, in agreement with the single-crystal structure described recently (Holbrey, J. D.; Reichert, W. M.; Nieuwenhuyzen, M.; Sheppard, O.; Hardacre, C.; Rogers, R. D. Chem. Commun. 2003, 476). In each case, the data was analyzed using an empirical potential structure refinement process.

Exporting Europeanisation to the Wider Europe: the Twinning Excercise and Administrative Reform in the Candidate Countries and Beyond

This article looks at the EU's efforts to assist administrative reform in Eastern Europe, with particular attention to the twinning exercise, conceptually linked to Europeanization. The article argues that much of the debate on Europeanization has focused predominantly on the way in which existing member states are being transformed as a result of their participation in EU structures. Yet the political importance attached to EU membership by the accession applicants, as well as EU's determination to ensure compliance with the acquis communautaire prior to entry, indicates that Europeanization is not only confined to existing EU member states, but can be exported outside the geographical borders of the EU. Against this background the article argues that extending the scope of the Europeanization thesis beyond existing members can not only help us understand better the process of transformation in Eastern Europe and the ongoing accession negotiations, but can also contribute towards the refinement of the term's rather blurred conceptual content.

Shifting of the electron-capture-to-the-continuum peak in proton-helium collisions at 10 and 20 keV

A refined theoretical approach has been developed to study the double-differential cross sections (DDCS's) in proton-helium collisions as a function of the ratio of ionized electron velocity to the incident proton velocity. The refinement is done in the present coupled-channel calculation by introducing a continuum distorted wave in the final state coupled with discrete states including direct as well as charge transfer channels. It is confirmed that the electron-capture-to-the-continuum (ECC) peak is slightly shifted to a lower electron velocity than the equivelocity position. Comparing measurements and classical trajectory Monte Carlo (CTMC) calculations at 10 and 20 keV proton energies, excellent agreement of the ECC peak heights is achieved at both energies. However, a minor disagreement in the peak positions between the present calculation and the CTMC results is noted. A smooth behavior of the DDCS is found in the present calculation on both sides of the peak whereas the CTMC results show some oscillatory behavior particularly to the left of the peak, associated with the statistical nature of CTMC calculations.

High-pressure deformation mechanism in scolecite: A combined computational-experimental study

Pressure-induced structural modifications in scolecite were studied by means of in situ synchrotron X-ray powder diffraction and density functional computations. The experimental cell parameters were refined up to 8.5 GPa. Discontinuities in the slope of the unit-cell parameters vs. pressure dependence were observed; as a consequence, an increase in the slope of the linear pressure-volume dependence is observed at about 6 GPa, suggesting an enhanced compressibility at higher pressures. Weakening and broadening of the diffraction peaks reveals increasing structural disorder with pressure, preventing refinement of the lattice parameters above 8.5 GPa. Diffraction patterns collected during decompression show that the disorder is irreversible. Atomic coordinates within unit cells of different dimensions were determined by means of Car-Parrinello simulations. The discontinuous rise in compressibility at about 6 GPa is reproduced by the computation, allowing us to attribute it to re-organization of the hydrogen bonding network, with the formation of water dimers. Moreover we found that, with increasing pressure, the tetrahedral chains parallel to c rotate along their elongation axis and display an increasing twisting along a direction perpendicular to c. At the same time, we observed the compression of the channels. We discuss the modification of the Ca polyhedra under pressure, and the increase in coordination number (from 4 to 5) of one of the two Al atoms, resulting from the approach of a water molecule. We speculate that this last transformation triggers the irreversible disordering of the system.

Fast Heating scalable to laser fusion ignition

Rapid heating of a compressed fusion fuel by a short-duration laser pulse is a promising route to generating energy by nuclear fusion1, and has been demonstrated on an experimental scale using a novel fast-ignitor geometry2. Here we describe a refinement of this system in which a much more powerful, pulsed petawatt (1015 watts) laser creates a fastheated core plasma that is scalable to fullscale ignition, significantly increasing the number of fusion events while still maintaining high heating efficiency at these substantially higher laser energies. Our findings bring us a step closer to realizing the production of relatively inexpensive, full-scale fast-ignition laser facilities.

A fast hybrid algorithm for exoplanetary transit searches

We present a fast and efficient hybrid algorithm for selecting exoplanetary candidates from wide-field transit surveys. Our method is based on the widely used SysRem and Box Least-Squares (BLS) algorithms. Patterns of systematic error that are common to all stars on the frame are mapped and eliminated using the SysRem algorithm. The remaining systematic errors caused by spatially localized flat-fielding and other errors are quantified using a boxcar-smoothing method. We show that the dimensions of the search-parameter space can be reduced greatly by carrying out an initial BLS search on a coarse grid of reduced dimensions, followed by Newton-Raphson refinement of the transit parameters in the vicinity of the most significant solutions. We illustrate the method's operation by applying it to data from one field of the SuperWASP survey, comprising 2300 observations of 7840 stars brighter than V = 13.0. We identify 11 likely transit candidates. We reject stars that exhibit significant ellipsoidal variations caused indicative of a stellar-mass companion. We use colours and proper motions from the Two Micron All Sky Survey and USNO-B1.0 surveys to estimate the stellar parameters and the companion radius. We find that two stars showing unambiguous transit signals pass all these tests, and so qualify for detailed high-resolution spectroscopic follow-up.

Unemployment Duration: Competing and Defective Risks

This paper examines the determinants of unemployment duration in a competing risks framework with two destination states: inactivity and employment. The innovation is the recognition of defective risks. A polynomial hazard function is used to differentiate between two possible sources of infinite durations. The first is produced by a random process of unlucky draws, the second by workers rejecting a destination state. The evidence favors the mover-stayer model over the search model. Refinement of the former approach, using a more flexible baseline hazard function, produces a robust and more convincing explanation for positive and zero transition rates out of unemployment.

Decay measures on locally compact abelian topological groups

Source: PROCEEDINGS OF THE ROYAL SOCIETY OF EDINBURGH SECTION A-MATHEMATICS Volume: 131 Pages: 1257-1273 Part: Part 6 Published: 2001 Times Cited: 5 References: 23 Citation MapCitation Map beta Abstract: We show that the Banach space M of regular sigma-additive finite Borel complex-valued measures on a non-discrete locally compact Hausdorff topological Abelian group is the direct sum of two linear closed subspaces M-D and M-ND, where M-D is the set of measures mu is an element of M whose Fourier transform vanishes at infinity and M-ND is the set of measures mu is an element of M such that nu is not an element of MD for any nu is an element of M \ {0} absolutely continuous with respect to the variation \mu\. For any corresponding decomposition mu = mu(D) + mu(ND) (mu(D) is an element of M-D and mu(ND) is an element of M-ND) there exist a Borel set A = A(mu) such that mu(D) is the restriction of mu to A, therefore the measures mu(D) and mu(ND) are singular with respect to each other. The measures mu(D) and mu(ND) are real if mu is real and positive if mu is positive. In the case of singular continuous measures we have a refinement of Jordan's decomposition theorem. We provide series of examples of different behaviour of convolutions of measures from M-D and M-ND.

Modelling the MAPK signalling pathway using a two-stage identification algorithm

Signal transduction pathways describe the dynamics of cellular response to input signalling molecules at receptors on the cell membrane. The Mitogen-Activated Protein Kinase (MAPK) cascade is one of such pathways that are involved in many important cellular processes including cell growth and proliferation. This paper describes a black-box model of this pathway created using an advanced two-stage identification algorithm. Identification allows us to capture the unique features and dynamics of the pathway and also opens up the possibility of regulatory control design. In the approach described, an optimal model is obtained by performing model subset selection in two stages, where the terms are first determined by a forward selection method and then modified using a backward selection model refinement. The simulation results demonstrate that the model selected using the two-stage algorithm performs better than with the forward selection method alone.

Liquid structure of the ionic liquid, 1-methyl-4-cyanopyridinium bis{(trifluoromethyl)sulfonyl}imide determined from neutron scattering and molecular dynamics simulations

The liquid structure of 1-methyl-4-cyanopyridinium bis {(trifluoromethyl)sulfonyl}imide, a prototypical ionic liquid containing an electron-withdrawing group on the cation, has been investigated at 368 K. Experimental neutron scattering combined with empirical potential structure refinement analysis of the data and classical molecular dynamics simulations have been used to probe the liquid structure in detail. Both techniques generated highly consistent results that provide valuable validation of the force fields and refinement approaches. A significant degree of apparent charge ordering is found in the liquid structure, although the nonspherical shape of the ions results in interpenetration of cations into the first shell of adjacent cations, with much shorter closest contact distances than the averaged center-of-mass cation-cation and cation-anion separations.

Liquid structure of 1, 3-dimethylimidazolium salts

The structure of liquid 1, 3-dimethylimidazolium hexafluorophosphate is described in detail and compared with the structure of 1, 3-dimethylimidazolium chloride. In each case, the data were obtained from neutron diffraction experiments and analysed using an empirical potential structure refinement process. Overall, the structures are similar; however, significant differences arise from the variation in anion size.

Semi-formal Models to Support Program Development: Autonomic Management within Component Based Parallel and Distributed Programming

Functional and non-functional concerns require different programming effort, different techniques and different methodologies when attempting to program efficient parallel/distributed applications. In this work we present a "programmer oriented" methodology based on formal tools that permits reasoning about parallel/distributed program development and refinement. The proposed methodology is semi-formal in that it does not require the exploitation of highly formal tools and techniques, while providing a palatable and effective support to programmers developing parallel/distributed applications, in particular when handling non-functional concerns.

Mechanism of Activation of a G Protein-coupled Receptor, the Human Cholecystokinin-2 Receptor

G protein-coupled receptors (GPCRs) represent a major focus in functional genomics programs and drug development research, but their important potential as drug targets contrasts with the still limited data available concerning their activation mechanism. Here, we investigated the activation mechanism of the cholecystokinin-2 receptor (CCK2R). The three-dimensional structure of inactive CCK2R was homology-modeled on the basis of crystal coordinates of inactive rhodopsin. Starting from the inactive CCK2R modeled structure, active CCK2R (namely cholecystokinin-occupied CCK2R) was modeled by means of steered molecular dynamics in a lipid bilayer and by using available data from other GPCRs, including rhodopsin. By comparing the modeled structures of the inactive and active CCK2R, we identified changes in the relative position of helices and networks of interacting residues, which were expected to stabilize either the active or inactive states of CCK2R. Using targeted molecular dynamics simulations capable of converting CCK2R from the inactive to the active state, we delineated structural changes at the atomic level. The activation mechanism involved significant movements of helices VI and V, a slight movement of helices IV and VII, and changes in the position of critical residues within or near the binding site. The mutation of key amino acids yielded inactive or constitutively active CCK2R mutants, supporting this proposed mechanism. Such progress in the refinement of the CCK2R binding site structure and in knowledge of CCK2R activation mechanisms will enable target-based optimization of nonpeptide ligands.

A heuristic model for the simulation of the deformation of elastic and spongy material for virtual reality applications

This paper presents a practical algorithm for the simulation of interactive deformation in a 3D polygonal mesh model. The algorithm combines the conventional simulation of deformation using a spring-mass-damping model, solved by explicit numerical integration, with a set of heuristics to describe certain features of the transient behaviour, to increase the speed and stability of solution. In particular, this algorithm was designed to be used in the simulation of synthetic environments where it is necessary to model realistically, in real time, the effect on non-rigid surfaces being touched, pushed, pulled or squashed. Such objects can be solid or hollow, and have plastic, elastic or fabric-like properties. The algorithm is presented in an integrated form including collision detection and adaptive refinement so that it may be used in a self-contained way as part of a simulation loop to include human interface devices that capture data and render a realistic stereoscopic image in real time. The algorithm is designed to be used with polygonal mesh models representing complex topology, such as the human anatomy in a virtual-surgery training simulator. The paper evaluates the model behaviour qualitatively and then concludes with some examples of the use of the algorithm.