Synthesis and X-ray crystal structure of a five-coordinate d8 complex: [Pt((Me2NN)(PMe2)(PPh2))2Cl][Cl]

C₃₆H₅₀Cl₂N₆P₄Pt·2 MeCN,2, triclinic P¯1,a=11.720(2),b=12.153(2),c=16.196(3),=76.74(1),=84.90(1),=88.13(1),Z=2,R=0.051,Rw=0.051. Interaction of Me₂NN(PMe₂)(PPh₂),1, with Pt(COD)Cl₂, COD=1,5 cyclooctadiene, in THF yields the title compound,2, in quantitative yield. Compound2 was characterized spectroscopically as well as via an X-ray diffraction study.     

Lorentz covariance and kinetic charge

There is a one-to-one correspondence between inequivalent covariant displaced Fock representations of the free relativistic field and the 1-cohomology of the Poincaré group with coefficients in the 1-particle space.Representations with positive energy are obtained from cocycles with finite energy which have particle-like properties and are interpreted as condensed states of matter without a sharply defined mass.The 1-cohomology groups ofP ₊ are calculated. These are trivial in 3- or 4-dimensional space-time, or if the mass is non-zero. Non-trivial cocycles for subgroups lead to representations in whichP-invariance is spontaneously broken. We recoverP-invariance in a direct integral representation possessing a gauge group, and a superselection structure labelled by the velocities of the condensed states of matter which are the cocycles determining each irreducible component of the representation. A model in 4-dimensional space-time is constructed.     

A comparison of the structures of vapour-deposited and bulk arsenic sulphide glasses

Accurate comparative measurements have been made of the X-ray diffraction pattern of a bulk arsenic sulphide glass prepared from the melt and a 250 μm film prepared by vapour deposition of the evaporated bulk. By using Ag Kα radiation, measurements have been made up to $\text{Q = 21}\text{A}\text{?}{}^{\mathrm{?1}}\text{(Q = 4π}\text{sin}\text{θ/λ)}$ so as to give good spatial resolution. Significant differences are found between bulk and film specimens, and in particular a shoulder is found on the high r side of the first peak in the distribution function for the film. Also, the film is richer in arsenic than the parent bulk. The results are compared in detail with a number of models, all of which involve covalent bonding requirements being fully satisfied, and it is concluded that there are more AsAs bonds in the film than the minimum required by stoichiometry and that a significant fraction ($\text{≈}\text{2}\text{3}$) of these are unusually long ($\text{≈2.6}\text{A}\text{?}$ compared to the more usual 2.5 Å). The most probable explanation is that the vapour contains a significant fraction of As₄S₄ species (in which the AsAs distances are $\text{≈2.6}\text{A}\text{?}$) and that the film contains a mixture of molecular species which have undergone considerable polymerization. The extent to which this results in a sheet-like structure similar to that proposed for the bulk glass remains unclear.     

Copper Binding and Oligomerization Studies of the Metal Resistance Determinant CrdA from Helicobacter pylori

Within this research, the CrdA protein from Helicobacter pylori (HpCrdA), a putative copper-binding protein important for the survival of bacterium, was biophysically characterized in a solution, and its binding affinity toward copper was experimentally determined. Incubation of HpCrdA with Cu(II) ions favors the formation of the monomeric species in the solution. The modeled HpCrdA structure shows a conserved methionine-rich region, a potential binding site for Cu(I), as in the structures of similar copper-binding proteins, CopC and PcoC, from Pseudomonas syringae and from Escherichia coli, respectively. Within the conserved amino acid motif, HpCrdA contains two additional methionines and two glutamic acid residues (MMXEMPGMXXMXEM) in comparison to CopC and PcoC but lacks the canonical Cu(II) binding site (two His) since the sequence has no His residues. The methionine-rich site is in a flexible loop and can adopt different geometries for the two copper oxidation states. It could bind copper in both oxidation states (I and II), but with different binding affinities, micromolar was found for Cu(II), and less than nanomolar is proposed for Cu(I). Considering that CrdA is a periplasmic protein involved in chaperoning copper export and delivery in the H. pylori cell and that the affinity of the interaction corresponds to a middle or strong metal–protein interaction depending on the copper oxidation state, we conclude that the interaction also occurs in vivo and is physiologically relevant for H. pylori.     

Supernovae and the Arrow of Time

Supernovae are explosions of stars and are a central problem in astrophysics. Rayleigh–Taylor (RT) and Richtmyer–Meshkov (RM) instabilities develop during the star’s explosion and lead to intense interfacial RT/RM mixing of the star materials. We handle the mathematical challenges of the RT/RM problem based on the group theory approach. We directly link the conservation laws governing RT/RM dynamics to the symmetry-based momentum model, derive the model parameters, and find the analytical solutions and characteristics of RT/RM dynamics with variable accelerations in the linear, nonlinear and mixing regimes. The theory outcomes explain the astrophysical observations and yield the design of laboratory experiments. They suggest that supernova evolution is a non-equilibrium process directed by the arrow of time.     

On the origin of compositional fluctuations in ZnSe1- x S x alloys grown by metal-organic vapour-phase epitaxy

Periodic vertical modulations of the sulphur concentration have been observed in epitaxial layers of ZnSe_{1? x} S _x grown by metal-organic vapour-phase epitaxy. High-spatial-resolution microanalysis has shown that the sulphur variation is of the order of 1 at.% with a period of about 44 ± 0.1 nm. A detailed analysis of the possible causes of this modulation is presented which shows that periodic temperature fluctuations of the substrate are the most likely source.     

Recent Trends in Polymer Electrolytes Based on Poly(Ethylene Oxide)

Recent work on the crystallographic and morphological structure of semicrystalline PEO complexes with alkali metal salts is described. The thermal properties of the materials and the influence of solvent on complex formation is also considered. The dependence of the ionic conductivity of the complexes on their morphology, the temperature and ionic association is discussed and some current work relating to the mechanism of conduction is considered. The various strategies which have been adopted to suppress crystallinity and so to optimize ionic conductivity, including networks, “comb” structures, and linear copolymers, are reviewed. The morphological organization and mesogenic behavior of some novel crystalline complexes of PEO with organo-alkali salts, such as sodium phenolates and naphtholates, are discussed. Some PEO composite materials which have mixed electronic-ionic mechanisms of conductivity are also described.     

Experimental versus predicted affinities for ligand binding to estrogen receptor: iterative selection and rescoring of docked poses systematically improves the correlation

The computational determination of binding modes for a ligand into a protein receptor is much more successful than the prediction of relative binding affinities (RBAs) for a set of ligands. Here we consider the binding of a set of 26 synthetic A-CD ligands into the estrogen receptor ERα. We show that the MOE default scoring function (London dG) used to rank the docked poses leads to a negligible correlation with experimental RBAs. However, switching to an energy-based scoring function, using a multiple linear regression to fit experimental RBAs, selecting top-ranked poses and then iteratively repeating this process leads to exponential convergence in 4–7 iterations and a very strong correlation. The method is robust, as shown by various validation tests. This approach may be of general use in improving the quality of predicted binding affinities.     

Experimental observation of modulation instability and optical spatial soliton arrays in soft condensed matter

In this Letter we report observations of optically induced self-organization of colloidal arrays in the presence of unpatterned counterpropagating evanescent waves. The colloidal arrays formed along the laser propagation axis are shown to be linked to the breakup of the incident field into optical spatial solitons, the lateral spacing of the arrays being related to modulation instability of the soft condensed matter system.