991 resultados para Structure of solids and liquids


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Chicken pancreatic polypeptide is the prototype of the neuropeptide Y (NPY)/PP superfamily of regulatory peptides. This polypeptide was appended the descriptive term avian, despite the presence of some 8600 extant species of bird. Additional primary structures from other avian species, including turkey, goose and ostrich, would suggest that the primary structure of this polypeptide has been highly-conserved during avian evolution. Avian pancreatic polypeptides structurally-characterised to date have distinctive primary structural features unique to this vertebrate group including an N-terminal glycyl residue and a histidyl residue at position 34. The crow family, Corvidae, is representative of the order Passeriformes, generally regarded as the most evolutionarily recent and diverse avian taxon. Pancreatic polypeptide has been isolated from pancreatic tissues from five representative Eurasian species (the magpie, Pica pica; the jay, Garrulus glandarius; the hooded crow, Corvus corone; the rook, Corvus frugilegus; the jackdaw, Corvus monedula) and subjected to structural analyses. Mass spectroscopy estimated the molecular mass of each peptide as 4166 +/- 2 Da. The entire primary structures of 36 amino acid residue peptides were established in single gas-phase sequencing runs. The primary structures of pancreatic polypeptides from all species investigated were identical: APAQPAYPGDDAPVEDLLR-FYNDLQQYLNVVTRPRY. The peptides were deemed to be amidated due to their full molar cross-reactivity with the amide-requiring PP antiserum employed. The molecular mass (4165.6 Da), calculated from the sequences, was in close agreement with mass spectroscopy estimates. The presence of an N-terminal alanyl residue and a prolyl residue at position 34 differentiates crow PP from counterparts in other avian species. These residues are analogous to those found in most mammalian analogues. These data suggest that the term avian, appended to the chicken peptide, is no longer tenable due to the presence of an Ala1, Pro34 peptide in five species from the largest avian order. These data might also suggest that, in keeping with the known structure/activity requirements of this peptide family, crow PP should interact identically to mammalian analogues on mammalian receptors.

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Burkholderia cenocepacia is an opportunistic pathogen that displays a remarkably high resistance to antimicrobial peptides. We hypothesize that high resistance to antimicrobial peptides in these bacteria is because of the barrier properties of the outer membrane. Here we report the identification of genes for the biosynthesis of the core oligosaccharide (OS) moiety of the B. cenocepacia lipopolysaccharide. We constructed a panel of isogenic mutants with truncated core OS that facilitated functional gene assignments and the elucidation of the core OS structure in the prototypic strain K56-2. The core OS structure consists of three heptoses in the inner core region, 3-deoxy-d-manno-octulosonic acid, d-glycero-d-talo-octulosonic acid, and 4-amino-4-deoxy-l-arabinose linked to d-glycero-d-talo-octulosonic acid. Also, glucose is linked to heptose I, whereas heptose II carries a second glucose and a terminal heptose, which is the site of attachment of the O antigen. We established that the level of core truncation in the mutants was proportional to their increased in vitro sensitivity to polymyxin B (PmB). Binding assays using fluorescent 5-dimethylaminonaphthalene-1-sulfonyl-labeled PmB demonstrated a correlation between sensitivity and increased binding of PmB to intact cells. Also, the mutant producing a heptoseless core OS did not survive in macrophages as compared with the parental K56-2 strain. Together, our results demonstrate that a complete core OS is required for full PmB resistance in B. cenocepacia and that resistance is due, at least in part, to the ability of B. cenocepacia to prevent binding of the peptide to the bacterial cell envelope.

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Experimental values for the solubility of carbon dioxide and hydrogen in three room temperature ionic liquids based on the same anion- (bistrifluoromethylsulfonyl)imide [Ntf2]-and three different cations-1-butyl-3-methylimidazolium, [C4mim], 1-ethyl-3- methylimidazolium, [C2mim] and trimethyl-butylammonium, [N 4111]-are reported between 283 and 343 K and close to atmospheric pressure. Carbon dioxide, with a mole-fraction solubility of the order of 10-2, is two orders of magnitude more soluble than hydrogen. The solubility of CO2 is very similar in the three ionic liquids although slightly lower in the presence of the [C2mim] cation. In the case of H2, noticeable differences were observed with larger mole fraction solubilities in the presence of [N4111] followed by [C 4mim]. All of the mole-fraction solubilities decrease with increasing temperature. From the variation of Henry's law constants with temperature, the thermodynamic functions of solvation were calculated. The precision of the experimental data, considered as the average absolute deviation of the Henry's law constants from appropriate smoothing equations, is always better than ±1%. © Springer Science+Business Media, LLC 2007.

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The prediction and management of ecosystem responses to global environmental change would profit from a clearer understanding of the mechanisms determining the structure and dynamics of ecological communities. The analytic theory presented here develops a causally closed picture for the mechanisms controlling community and population size structure, in particular community size spectra, and their dynamic responses to perturbations, with emphasis on marine ecosystems. Important implications are summarised in non-technical form. These include the identification of three different responses of community size spectra to size-specific pressures (of which one is the classical trophic cascade), an explanation for the observed slow recovery of fish communities from exploitation, and clarification of the mechanism controlling predation mortality rates. The theory builds on a community model that describes trophic interactions among size-structured populations and explicitly represents the full life cycles of species. An approximate time-dependent analytic solution of the model is obtained by coarse graining over maturation body sizes to obtain a simple description of the model steady state, linearising near the steady state, and then eliminating intraspecific size structure by means of the quasi-neutral approximation. The result is a convolution equation for trophic interactions among species of different maturation body sizes, which is solved analytically using a novel technique based on a multiscale expansion.

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The electronic band structure of vacuum cleaved single-crystal indium selenide has been investigated by X-ray and ultraviolet photoelectron spectroscopy. The valence band consists of three well separated groups, one derived from the Se 4s levels, and two derived from p-like wavefunctions. The band structure and valence band density of states has been calculated using a tight-binding single-layer approximation and all the major features in the experimental spectra are well accounted for. The spin-orbit splitting and electron loss structure associated with the In 4d core level is also reported.

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The band structure of CdI has been calculated using a modified semi-empirical tight-binding method and the results obtained have been compared with both angularly averaged and angularly resolved photoemission spectra. The theoretically computed density of states distribution is in excellent agreement with angularly averaged results and all the main features observed experimentally are reproduced in the theory. Angularly resolved spectra have been used to draw up energy band dispersion curves directly and agreement with calculated bands in both the Gamma M and Gamma K directions of the Brillouin zone is good.

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A Cu/ZnO/Al2O3 commercial catalyst for methanol synthesis from syngas was investigated under operational conditions. HERFD XAS and EXAFS data were recorded under different reaction gas mixtures, temperatures, and pressures. Activation of the catalyst precursor occurred via a Cu+ intermediate. The active catalyst predominantly consists of metallic Cu and ZnO. Methanol production only starts when all accessible Cu is reduced. The structure of the active catalyst did not change with temperature or pressure even though the methanol yield changed strongly. Formation of a carbon-containing layer on top of the catalyst surface was detected by TPD, which was correlated with a several-hour induction period in the methanol production after the catalyst reduction.

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An extensive investigation of the ferromagnetic compound TlCo2S2 has resulted in new information on the electronic and magnetic structure. Electronic structure calculations showed that magnetic ordering is energetically favorable with a clear driving force for ferromagnetic coupling within the cobalt layers. TlCo2S2 is metallic and the conductivity is due to holes in the valence band. XPS single crystal measurements did not show evidence of mixed oxidation states of cobalt. Neutron powder diffraction resulted in a ferromagnetic structure with the magnetic moment in the ab-plane. The derived magnetic moment of the cobalt atom is 0.65(2) mu(B) at 10 K and is in very good agreement with the value, mu(sat) = 0.65(1) mu(B) at 10 K, inferred from the magnetic hysteresis curve. (C) 2004 Elsevier Inc. All rights reserved.

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A new ternary Ir-Mn-Si phase with stoichiometry Mn3IrSi has been synthesized and found to crystallize in the cubic AlAu4-type structure, space group P213 with Z=4, which is an ordered form of the beta-Mn structure. The unit cell dimension was determined by x-ray powder diffraction to a=6.4973(3) Angstrom. In addition to the crystal structure, we have determined the magnetic structure and properties using superconducting quantum interference device magnetometry and Rietveld refinements of neutron powder diffraction data. A complex noncollinear magnetic structure is found, with magnetic moments of 2.97(4)u(B) at 10 K only on the Mn atoms. The crystal structure consists of a triangular network built up by Mn atoms, on which the moments are rotated 120degrees around the triangle axes. The magnetic unit cell is the same as the crystallographic and carries no net magnetic moment. The Neel temperature was determined to be 210 K. A first-principles study, based on density functional theory in a general noncollinear formulation, reproduces the experimental results with good agreement. The observed magnetic structure is argued to be the result of frustration of antiferromagnetic couplings by the triangular geometry.

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The UV spectra of nova-like variables are dominated by emission from the accretion disk, modified by scattering in a wind emanating from the disk. Here, we model the spectra of RW Tri and UX UMa, the only two eclipsing nova-like variables which have been observed with the Hubble Space Telescope in the far-ultraviolet, in an attempt to constrain the geometry and the ionization structure of their winds. Using our Monte Carlo radiative transfer code, we computed spectra for simply parameterized axisymmetric biconical outflow models and were able to find plausible models for both systems. These reproduce the primary UV resonance lines-N v, Si iv, and C iv-in the observed spectra in and out of eclipse. The distribution of these ions in the wind models is similar in both cases as is the extent of the primary scattering regions in which these lines are formed. The inferred mass-loss rates are 6%-8% of the mass accretion rates for the systems. We discuss the implication of our point models for our understanding of accretion disk winds in cataclysmic variables. © 2010. The American Astronomical Society. All rights reserved.

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Nonrelativistic electrostatic unmagnetized shocks are frequently observed in laboratory plasmas and they are likely to exist in astrophysical plasmas. Their maximum speed, expressed in units of the ion acoustic speed far upstream of the shock, depends only on the electron-to-ion temperature ratio if binary collisions are absent. The formation and evolution of such shocks is examined here for a wide range of shock speeds with particle-in-cell simulations. The initial temperatures of the electrons and the 400 times heavier ions are equal. Shocks form on electron time scales at Mach numbers between 1.7 and 2.2. Shocks with Mach numbers up to 2.5 form after tens of inverse ion plasma frequencies. The density of the shock-reflected ion beam increases and the number of ions crossing the shock thus decreases with an increasing Mach number, causing a slower expansion of the downstream region in its rest frame. The interval occupied by this ion beam is on a positive potential relative to the far upstream. This potential pre-heats the electrons ahead of the shock even in the absence of beam instabilities and decouples the electron temperature in the foreshock ahead of the shock from the one in the far upstream plasma. The effective Mach number of the shock is reduced by this electron heating. This effect can potentially stabilize nonrelativistic electrostatic shocks moving as fast as supernova remnant shocks.