New insights into the compressibility and high-pressure stability of Ni(CN)2: a combined study of neutron diffraction, Raman spectroscopy, and inelastic neutron scattering

Nickel cyanide is a layered material showing markedly anisotropic behaviour. High-pressure neutron diffraction measurements show that at pressures up to 20.1 kbar, compressibility is much higher in the direction perpendicular to the layers, c, than in the plane of the strongly chemically bonded metal-cyanide sheets. Detailed examination of the behaviour of the tetragonal lattice parameters, a and c, as a function of pressure reveal regions in which large changes in slope occur, for example, in c(P) at 1 kbar. The experimental pressure dependence of the volume data is fitted to a bulk modulus, B0, of 1050 (20) kbar over the pressure range 0–1 kbar, and to 124 (2) kbar over the range 1–20.1 kbar. Raman spectroscopy measurements yield additional information on how the structure and bonding in the Ni(CN)2 layers change with pressure and show that a phase change occurs at about 1 kbar. The new high-pressure phase, (Phase PII), has ordered cyanide groups with sheets of D4h symmetry containing Ni(CN)4 and Ni(NC)4 groups. The Raman spectrum of phase PII closely resembles that of the related layered compound, Cu1/2Ni1/2(CN)2, which has previously been shown to contain ordered C≡N groups. The phase change, PI to PII, is also observed in inelastic neutron scattering studies which show significant changes occurring in the phonon spectra as the pressure is raised from 0.3 to 1.5 kbar. These changes reflect the large reduction in the interlayer spacing which occurs as Phase PI transforms to Phase PII and the consequent increase in difficulty for out-of-plane atomic motions. Unlike other cyanide materials e.g. Zn(CN)2 and Ag3Co(CN)6, which show an amorphization and/or a decomposition at much lower pressures (~100 kbar), Ni(CN)2 can be recovered after pressurising to 200 kbar, albeit in a more ordered form.

Measurement of the epicycle frequency in the Galactic disc and initial velocities of open clusters

A new method to measure the epicycle frequency kappa in the Galactic disc is presented. We make use of the large data base on open clusters completed by our group to derive the observed velocity vector (amplitude and direction) of the clusters in the Galactic plane. In the epicycle approximation, this velocity is equal to the circular velocity given by the rotation curve, plus a residual or perturbation velocity, of which the direction rotates as a function of time with the frequency kappa. Due to the non-random direction of the perturbation velocity at the birth time of the clusters, a plot of the present-day direction angle of this velocity as a function of the age of the clusters reveals systematic trends from which the epicycle frequency can be obtained. Our analysis considers that the Galactic potential is mainly axis-symmetric, or in other words, that the effect of the spiral arms on the Galactic orbits is small; in this sense, our results do not depend on any specific model of the spiral structure. The values of kappa that we obtain provide constraints on the rotation velocity of the in particular, V(0) is found to be 230 +/- 15 km s(-1) even if the scale (R(0) = 7.5 kpc) of the Galaxy is adopted. The measured kappa at the solar radius is 43 +/- 5 km s(-1) kpc(-1). The distribution of initial velocities of open clusters is discussed.

The spiral structure of the Galaxy revealed by CS sources and evidence for the 4:1 resonance

We present a map of the spiral structure of the Galaxy, as traced by molecular carbon monosulphide (CS) emission associated with IRAS sources which are believed to be compact H II regions. The CS line velocities are used to determine the kinematic distances of the sources in order to investigate their distribution in the galactic plane. This allows us to use 870 objects to trace the arms, a number larger than that of previous studies based on classical H II regions. The distance ambiguity of the kinematic distances, when it exists, is solved by different procedures, including the latitude distribution and an analysis of the longitude-velocity diagram. The study of the spiral structure is complemented with other tracers: open clusters, Cepheids, methanol masers and H II regions. The well-defined spiral arms are seen to be confined inside the corotation radius, as is often the case in spiral galaxies. We identify a square-shaped sub-structure in the CS map with that predicted by stellar orbits at the 4:1 resonance (four epicycle oscillations in one turn around the galactic centre). The sub-structure is found at the expected radius, based on the known pattern rotation speed and epicycle frequency curve. An inner arm presents an end with strong inwards curvature and intense star formation that we tentatively associate with the region where this arm surrounds the extremity of the bar, as seen in many barred galaxies. Finally, a new arm with concave curvature is found in the Sagitta to Cepheus region of the sky. The observed arms are interpreted in terms of perturbations similar to grooves in the gravitational potential of the disc, produced by crowding of stellar orbits.

A FOSSIL BULGE GLOBULAR CLUSTER REVEALED BY VERY LARGE TELESCOPE MULTI-CONJUGATE ADAPTIVE OPTICS

The globular cluster HP 1 is projected on the bulge, very close to the Galactic center. The Multi-Conjugate Adaptive Optics Demonstrator on the Very Large Telescope allowed us to acquire high-resolution deep images that, combined with first epoch New Technology Telescope data, enabled us to derive accurate proper motions. The cluster and bulge fields` stellar contents were disentangled through this process and produced an unprecedented definition in color-magnitude diagrams of this cluster. The metallicity of [Fe/H] approximate to -1.0 from previous spectroscopic analysis is confirmed, which together with an extended blue horizontal branch imply an age older than the halo average. Orbit reconstruction results suggest that HP 1 is spatially confined within the bulge.

VISTA Variables in the Via Lactea (VVV): The public ESO near-IR variability survey of the Milky Way

We describe the public ESO near-IR variability survey (VVV) scanning the Milky Way bulge and an adjacent section of the mid-plane where star formation activity is high. The survey will take 1929 h of observations with the 4-m VISTA telescope during 5 years (2010-2014), covering similar to 10(9) point sources across an area of 520 deg(2), including 33 known globular clusters and similar to 350 open clusters. The final product will be a deep near-IR atlas in five passbands (0.9-2.5 mu m) and a catalogue of more than 106 variable point sources. Unlike single-epoch surveys that, in most cases, only produce 2-D maps, the VVV variable star survey will enable the construction of a 3-D map of the surveyed region using well-understood distance indicators such as RR Lyrae stars, and Cepheids. It will yield important information on the ages of the populations. The observations will be combined with data from MACHO, OGLE, EROS, VST, Spitzer, HST, Chandra, INTEGRAL, WISE, Fermi LAT, XMM-Newton, GAIA and ALMA for a complete understanding of the variable sources in the inner Milky Way. This public survey will provide data available to the whole community and therefore will enable further studies of the history of the Milky Way, its globular cluster evolution, and the population census of the Galactic Bulge and center, as well as the investigations of the star forming regions in the disk. The combined variable star catalogues will have important implications for theoretical investigations of pulsation properties of stars. (C) 2009 Elsevier B.V. All rights reserved.

Revisiting 2D numerical models for the 19th century outbursts of eta Carinae

We present here new results of two-dimensional hydrodynamical simulations of the eruptive events of the 1840s (the great) and the 1890s (the minor) eruptions suffered by the massive star eta Carinae (Car). The two bipolar nebulae commonly known as the Homunculus and the little Homunculus (LH) were formed from the interaction of these eruptive events with the underlying stellar wind. We assume here an interacting, non-spherical multiple-phase wind scenario to explain the shape and the kinematics of both Homunculi, but adopt a more realistic parametrization of the phases of the wind. During the 1890s eruptive event, the outflow speed decreased for a short period of time. This fact suggests that the LH is formed when the eruption ends, from the impact of the post-outburst eta Car wind (that follows the 1890s event) with the eruptive flow (rather than by the collision of the eruptive flow with the pre-outburst wind, as claimed in previous models; Gonzalez et al.). Our simulations reproduce quite well the shape and the observed expansion speed of the large Homunculus. The LH (which is embedded within the large Homunculus) becomes Rayleigh-Taylor unstable and develop filamentary structures that resemble the spatial features observed in the polar caps. In addition, we find that the interior cavity between the two Homunculi is partially filled by material that is expelled during the decades following the great eruption. This result may be connected with the observed double-shell structure in the polar lobes of the eta Car nebula. Finally, as in previous work, we find the formation of tenuous, equatorial, high-speed features that seem to be related to the observed equatorial skirt of eta Car.

Cross-entropy optimizer: a new tool to study precession in astrophysical jets

Evidence of jet precession in many galactic and extragalactic sources has been reported in the literature. Much of this evidence is based on studies of the kinematics of the jet knots, which depends on the correct identification of the components to determine their respective proper motions and position angles on the plane of the sky. Identification problems related to fitting procedures, as well as observations poorly sampled in time, may influence the follow-up of the components in time, which consequently might contribute to a misinterpretation of the data. In order to deal with these limitations, we introduce a very powerful statistical tool to analyse jet precession: the cross-entropy method for continuous multi-extremal optimization. Only based on the raw data of the jet components (right ascension and declination offsets from the core), the cross-entropy method searches for the precession model parameters that better represent the data. In this work we present a large number of tests to validate this technique, using synthetic precessing jets built from a given set of precession parameters. With the aim of recovering these parameters, we applied the cross-entropy method to our precession model, varying exhaustively the quantities associated with the method. Our results have shown that even in the most challenging tests, the cross-entropy method was able to find the correct parameters within a 1 per cent level. Even for a non-precessing jet, our optimization method could point out successfully the lack of precession.

Further probing the nature of FSR 1767

With Two-Micron All-Sky Survey (2MASS) photometry and proper motions, Bonatto et al. suggested that FSR 1767 is a globular cluster (GC), while with J and K NTT/SOFI photometry Froebrich, Meusinger & Scholz concluded that it is not a star cluster. In this study, we combine previous and new evidence that are consistent with a GC. For instance, we show that the horizontal branch (HB) and red giant branch (RGB) stars, besides sharing a common proper motion, have radial density profiles that consistently follow the King`s law independently. Reddening maps around FSR 1767 are built using the bulge RGB as reference and also Schlegel`s extinction values to study local absorptions. Both approaches provide similar maps and show that FSR 1767 is not located in a dust window, which otherwise might have produced the stellar overdensity. Besides, neighbouring regions of similar reddening as FSR 1767 do not present the blue HB stars that are a conspicuous feature in the colour-magnitude diagram of FSR 1767. We report the presence of a compact group of stars located in the central parts of FSR 1767. It appears to be a detached post-collapse core, similar to those of other nearby low-luminosity GCs projected towards the bulge. We note that while the NTT/SOFI photometry of the star cluster FSR 1716 matches perfectly that from 2MASS, it shows a considerable offset for FSR 1767. We discuss the possible reasons why both photometries differ. We confirm our previous structural and photometric fundamental parameters for FSR 1767, which are consistent with a GC.

Thermal Phase Behavior of DMPG Bilayers in Aqueous Dispersions as Revealed by (2)H- and (31)P-NMR

The synthetic lipid 1,2-dimyristoyl-sn-3-phosphoglycerol (DMPG), when dispersed in water/NaCl exhibits a complex phase behavior caused by its almost unlimited swelling in excess water. Using deuterium ((2)H)- and phosphorus ((31)P)-NMR we have studied the molecular properties of DMPG/water/NaCl dispersions as a function of lipid and NaCl concentration. We have measured the order profile of the hydrophobic part of the lipid bilayer with deuterated DMPG while the orientation of the phosphoglycerol headgroup was deduced from the (31)P NMR chemical shielding anisotropy. At temperatures > 30 degrees C we observe well-resolved (2)H- and (31)P NMR spectra not much different from other liquid crystalline bilayers. From the order profiles it is possible to deduce the average length of the flexible fatty acyl chain. Unusual spectra are obtained in the temperature interval of 20-25 degrees C, indicating one or several phase transitions. The most dramatic changes are seen at low lipid concentration and low ionic strength. Under these conditions and at 25 degrees C, the phosphoglycerol headgroup rotates into the hydrocarbon layer and the hydrocarbon chains show larger flexing motions than at higher temperatures. The orientation of the phosphoglycerol headgroup depends on the bilayer surface charge and correlates with the degree of dissociation of DMPG-Na(+). The larger the negative surface charge, the more the headgroup rotates toward the nonpolar region.

Combining structure and dynamics: non-denaturing high-pressure effect on lysozyme in solution

Small-angle X-ray scattering (SAXS) and elastic and quasi-elastic neutron scattering techniques were used to investigate the high-pressure-induced changes on interactions, the low-resolution structure and the dynamics of lysozyme in solution. SAXS data, analysed using a global-fit procedure based on a new approach for hydrated protein form factor description, indicate that lysozyme completely maintains its globular structure up to 1500 bar, but significant modi. cations in the protein-protein interaction potential occur at approximately 600-1000 bar. Moreover, the mass density of the protein hydration water shows a clear discontinuity within this pressure range. Neutron scattering experiments indicate that the global and the local lysozyme dynamics change at a similar threshold pressure. A clear evolution of the internal protein dynamics from diffusing to more localized motions has also been probed. Protein structure and dynamics results have then been discussed in the context of protein-water interface and hydration water dynamics. According to SAXS results, the new configuration of water in the first hydration layer induced by pressure is suggested to be at the origin of the observed local mobility changes.

A Multitechnique Study of Structure and Dynamics of Polyfluorene Cast Films and the Influence on Their Photoluminescence

This article describes the microstructure and dynamics in the solid state of polyfluorene-based polymers, poly(9,)-dioctylfluorenyl-2,7-diyl) (PFO), a semicrystalline polymer, and poly [(9,9-dioctyl- 2,7-divinylene-fluorenylene)-alt-co-{2-methoxy-5-(2-ethyl-hexyloxy)- 1,4-phenylene vinylene}, a copolymer with mesomorphic phase properties. These Structures were determined by wide-angle X-ray scattering (WAXS) measurements, Assuming a packing model for the copolymer structure, where the planes of the phenyl rings are stacked and separated by an average distance of similar to 4.5 angstrom and laterally spaced by about similar to 16 angstrom, we followed the evolution of these distances as a function of temperature using WAXS and associated the changes observed to the polymer relaxation processes identified by dynamical mechanical thermal analysis. Specific molecular motions were studied by solid-state nuclear magnetic resonance. The onset of the side-chain motion at about 213 K (beta-relaxation) produced a small increase in the lateral spacing and in the stacking distance of the phenyl rings in them aggregated Structures, Besides, at about 383 K (alpha-relaxation) there occurs a significant increase in the amplitude of the torsion motion in the backbone, producing a greater increase in the stacking distance of the phenyl rings. Similar results were observed in the semicrystalline phase of PFO, but in this case the presence of the crystalline structure affects considerably the overall dynamics, which tends to be more hindered. Put together, Our data explain many features of the temperature dependence of the photoluminescence of these two polymers.

Temperature dependence of molecular dynamics and supramolecular aggregation in MEH-PPV films: A solid-state NMR, X-ray and fluorescence spectroscopy study

This article presents an investigation of the temperature induced modification in the microstructure and dynamics of poly[2-methoxy-5-(2`-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) cast films using Wide-Angle X-ray Scattering (WAXS), solid-state Nuclear Magnetic Resonance (NMR), and Fluorescence Spectroscopy (PL). MEH-PPV chain motions were characterized as a function of temperature by NMR. The results indicated that the solvent used to cast the films influences the activation energy of the side-chain motions. This was concluded from the comparison of the activation energy of the toluene cast film, E(a) = (54 +/- 8) kJ/mol, and chloroform cast film, E(a) = (69 +/- 5) kJ/mol, and could be attributed to the higher side-chain packing provided by chloroform, that preferentially solvates the side chain in contrast to toluene that solvates mainly the backbone. Concerning the backbone mobility, it was observed that the torsional motions in the MEH-PPV have average amplitude of similar to 10 degrees at 300 K, which was found to be independent of the solvent used to cast the films. In order to correlate the molecular dynamics processes with the changes in the microstructure of the polymer, in situ WAXS experiments as a function of temperature were performed and revealed that the interchain spacing in the MEH-PPV molecular aggregates increases as a function of temperature, particularly at temperatures where molecular relaxations occur. It was also observed that the WAXS peak associated with the bilayer spacing becomes narrower and its intensity increases whereas the peak associated with the inter-backbone planes reduces its intensity for higher temperatures. This last result Could be interpreted as a decrease in the number of aggregates and the reduction of the interchain species during the MEH-PPV relaxation processes. These WAXS results were correlated with PL spectra modifications observed upon temperature treatments. (C) 2008 Elsevier Ltd. All rights reserved.

Crystallographic Structure of Phosphofructokinase-2 from Escherichia coli in Complex with Two ATP Molecules. Implications for Substrate Inhibition

Phosphofructokinase-1 and -2 (Pfk-1 and Pfk-2, respectively) from Escherichia coli belong to different homologous superfamilies. However, in spite of the lack of a common ancestor, they share the ability to catalyze the same reaction and are inhibited by the substrate MgATP. Pfk-2, an ATP-dependent 6-phosphofructokinase member of the ribokinase-like superfamily, is a homodimer of 66 kDa subunits whose oligomerization state is necessary for catalysis and stability. The presence of MgATP favors the tetrameric form of the enzyme. In this work, we describe the structure of Pfk-2 in its inhibited tetrameric form, with each subunit bound to two ATP molecules and two Mg ions. The present structure indicates that substrate inhibition occurs due to the sequential binding of two MgATP molecules per subunit, the first at the usual site occupied by the nucleotide in homologous enzymes and the second at the allosteric site, making a number of direct and Mg-mediated interactions with the first. Two configurations are observed for the second MgATP, one of which involves interactions with Tyr23 from the adjacent subunit in the dimer and the other making an unusual non-Watson-Crick base pairing with the adenine in the substrate ATP. The oligomeric state observed in the crystal is tetrameric, and some of the structural elements involved in the binding of the Substrate and allosteric ATPs are also participating in the dimer-dimer interface. This structure also provides the grounds to compare analogous features of the nonhomologous phosphofructokinases from E. coli. (C) 2008 Elsevier Ltd. All rights reserved.

Only subtle protein conformational adaptations are required for ligand binding to thyroid hormone receptors: Simulations using a novel multipoint steered molecular dynamics approach

Thyroid hormone receptors (TR) are hormone-dependent transcription regulators that play a major role in human health, development, and metabolic functions. The thyroid hormone resistance syndrome, diabetes, obesity, and some types of cancer are just a few examples of important diseases that are related to TR malfunctioning, particularly impaired hormone binding. Ligand binding to and dissociation from the receptor ultimately control gene transcription and, thus, detailed knowledge of binding and release mechanisms are fundamental for the comprehension of the receptor`s biological function and development of pharmaceuticals. In this work, we present the first computational study of ligand entry into the ligand binding domain (LBD) of a nuclear receptor. We report molecular dynamics simulations of ligand binding to TRs using a generalization of the steered molecular dynamics technique designed to perform single-molecule pulling simulations along arbitrarily nonlinear driving pathways. We show that only gentle protein movements and conformational adaptations are required for ligand entry into the LBDs and that the magnitude of the forces applied to assist ligand binding are of the order of the forces involved in ligand dissociation. Our simulations suggest an alternative view for the mechanisms ligand binding and dissociation of ligands from nuclear receptors in which ligands can simply diffuse through the protein surface to reach proper positioning within the binding pocket. The proposed picture indicates that the large-amplitude protein motions suggested by the apo- and holo-RXR alpha crystallographic structures are not required, reconciling conformational changes of LBDs required for ligand entry with other nuclear receptors apo-structures that resemble the ligand-bound LBDs.

A study of the relaxation dynamics in a quadrupolar NMR system using Quantum State Tomography

This article reports a relaxation study in an oriented system containing spin 3/2 nuclei using quantum state tomography (QST). The use of QST allowed evaluating the time evolution of all density matrix elements starting from several initial states. Using an appropriated treatment based on the Redfield theory, the relaxation rate of each density matrix element was measured and the reduced spectral densities that describe the system relaxation were determined. All the experimental data could be well described assuming pure quadrupolar relaxation and reduced spectral densities corresponding to a superposition of slow and fast motions. The data were also analyzed in the context of Quantum Information Processing, where the coherence loss of each qubit of the system was determined using the partial trace operation. (C) 2008 Elsevier Inc. All rights reserved.