Role of two consecutive alpha,beta-dehydrophenylalanines in peptide structure: Crystal and molecular structure of Boc-Leu-Delta Phe-Delta Phe-Ala-Phe-NHMe

An N-alpha-protected model pentapeptide containing two consecutive Delta Phe residues, Boc-Leu-Delta Phe-Delta Phe-Ala-Phe-NHMe, has been synthesized by solution methods and fully characterized. H-1-nmr studies provided evidence for the occurrence of a significant population of a conformer having three consecutive, intramolecularly II-bonded beta-bends in solution. The solid state structure has been determined by x-ray diffraction methods. The crystals grown from aqueous methanol are orthorhombic, space group P2(1)2(1)2(1),, a = 11.503(2), b = 16.554(2), c = 22.107(3) Angstrom, V = 4209(1) Angstrom,(3) and Z = 4. The x-ray data were collected on a CAD4 diffractometer using CuKalpha radiation (lambda = 1.5418 Angstrom). The structure was determined using direct methods and refined by full-matrix least-squares procedure. The R factor is 5.3%. The molecule is characterized by a right handed 3(10)-helical conformation ((phi) = -68.2 degrees (psi) = -26.3 degrees), which is made up of two consecutive type III beta-bends and one type I beta-bend. In the solid state the helical molecules are aligned head-to-tail, thus forming long rod like structures. A comparison with other peptide structures containing consecutive Delta Phe residues is also provided. The present study confirms that the -Delta Phe-Delta Phe-sequence can be accommodated in helical structures. (C) 1997 John Wiley & Sons, Inc.

Superconducting YBa2Cu3O7-delta thick films on Ba2RETaO6 (RE=Pr, Nd, Eu, and Dy) substrates

Thick films of YBa2Cu3O7-delta fabricated on polycrystalline Ba2RETaO6 (where RE= Pr, Nd, Eu, and Dy) substrates by dip-coating and partial melting techniques are textured and c-axis oriented, showing predominantly (00l) orientation. All the thick films show a superconducting zero resistance transition of 90 K. SEM studies clearly indicate platelike and needlelike grain growth over a wide area of the thick films. The values of the critical current density for these thick films are similar to 10(4) A/cm(2) at 77 K as determined by the nonresonant R.F. absorption method. Various processing conditions that affect the critical current density of thick films are also discussed.

The log delta log t method for the determination of the coefficient of consolidation

The behaviour of saturated soils undergoing consolidation is very complex, It may not follow Terzaghi's theory over the entire consolidation process, Different soils may behave in such a way as to fit into Terzaghi's theory over some specific stages of the consolidation process (percentage of consolidation), This may be one of the reasons for the difficulties faced by the existing curve-fitting procedures in obtaining the coefficient of consolidation, c(v). It has been shown that the slope of the initial linear portion of the theoretical log U-log T curve is constant over a wider range of degree of consolidation, U, when compared with the other methods in use, This initial well-defined straight line in the log U-log T plot intersects the U = 100% line at T = pi/4, which corresponds to U = 88.3%, The proposed log delta-log t method is based on this observation, which gives the value of c(v) through simple graphical construction, In the proposed method, which is more versatile, identification of the characteristic straight lines is very clear; the intersection of these lines is more precise and the method does not depend upon the initial compression for the determination of c(v).

Magnetoresistance of the metallic perovskite oxide LaNiO3-delta

We report a study of the magnetoresistance (MR) of the metallic perovskite oxide LaNiO3-delta as a function of the oxygen stoichiometry delta (delta less than or equal to 0.14), magnetic field (H less than or equal to 6 T) and temperature (1.5 K less than or equal to T less than or equal to 25 K). We find a strong dependence of the nature of the MR on the oxygen stoichiometry. The MR at low temperatures changes from positive to negative as the sample becomes more oxygen deficient (i.e. delta increases). Some of the samples, which are more resistive, show resistivity minima at T-min approximate to 20 K. We find that in these samples the MR is positive for T > T-min and negative for T < T-min. We conclude that in the absence of strong magnetic interaction, the negative MR in these oxides can arise from weak-localization effects.

Structure of basic winged-bean lectin and a comparison with its saccharide-bound form

The crystal structure of the saccharide-free form of the basic form of winged-bean agglutinin (WBAI) has been solved by the molecular-replacement method and refined at 2.3 Angstrom resolution The final R factor is 19.74b for all data in the resolution range 8.0-2.3 Angstrom. The asymmetric unit contains two half-dimers, each located on a crystallographic twofold axis. The structure of the saccharide-free form is compared with that of the complex of WBAI wi th methyl-alpha-D-galactoside. The complex is composed of two dimers in the asymmetric unit. The intersubunit interactions in the dimer are nearly identical in the two structures The binding site of the saccharide-free structure contains three ordered water molecules at positions similar to those of the hydroxyl groups of the carbohydrate which an hydrogen bonded to the protein. Superposition of the saccharide-binding sites of the two structures shows that the major changes involve expulsion of these ordered water molecules and a shift of about 0.6 Angstrom of the main-chain atoms of the variable loop.

Thermal expansion of LaBa2Cu2CoO7+delta

In this paper, we report high-temperature X-ray diffraction (HTXRD) and dilatometric studies on LaBa2Cu2CoO7+delta. Bulk and volume thermal expansion studies, along with a study of its phase transition, were carried out. The linear and volume thermal expansion coefficients were found to be 11.7 X 10(-6) K-1 and 42.3 X 10(-6) K-1, respectively. (C) 2000 Elsevier Science Ltd.

Velocity distribution for a dilute vibrated granular material

The velocity distribution for a vibrated granular material is determined in the dilute limit where the frequency of particle collisions with the vibrating surface is large compared to the frequency of binary collisions. The particle motion is driven by the source of energy due to particle collisions with the vibrating surface, and two dissipation mechanisms-inelastic collisions and air drag-are considered. In the latter case, a general form for the drag force is assumed. First, the distribution function for the vertical velocity for a single particle colliding with a vibrating surface is determined in the limit where the dissipation during a collision due to inelasticity or between successive collisions due to drag is small compared to the energy of a particle. In addition, two types of amplitude functions for the velocity of the surface, symmetric and asymmetric about zero velocity, are considered. In all cases, differential equations for the distribution of velocities at the vibrating surface are obtained using a flux balance condition in velocity space, and these are solved to determine the distribution function. It is found that the distribution function is a Gaussian distribution when the dissipation is due to inelastic collisions and the amplitude function is symmetric, and the mean square velocity scales as [[U-2](s)/(1 - e(2))], where [U-2](s) is the mean square velocity of the vibrating surface and e is the coefficient of restitution. The distribution function is very different from a Gaussian when the dissipation is due to air drag and the amplitude function is symmetric, and the mean square velocity scales as ([U-2](s)g/mu(m))(1/(m+2)) when the acceleration due to the fluid drag is -mu(m)u(y)\u(y)\(m-1), where g is the acceleration due to gravity. For an asymmetric amplitude function, the distribution function at the vibrating surface is found to be sharply peaked around [+/-2[U](s)/(1-e)] when the dissipation is due to inelastic collisions, and around +/-[(m +2)[U](s)g/mu(m)](1/(m+1)) when the dissipation is due to fluid drag, where [U](s) is the mean velocity of the surface. The distribution functions are compared with numerical simulations of a particle colliding with a vibrating surface, and excellent agreement is found with no adjustable parameters. The distribution function for a two-dimensional vibrated granular material that includes the first effect of binary collisions is determined for the system with dissipation due to inelastic collisions and the amplitude function for the velocity of the vibrating surface is symmetric in the limit delta(I)=(2nr)/(1 - e)much less than 1. Here, n is the number of particles per unit width and r is the particle radius. In this Limit, an asymptotic analysis is used about the Limit where there are no binary collisions. It is found that the distribution function has a power-law divergence proportional to \u(x)\((c delta l-1)) in the limit u(x)-->0, where u(x) is the horizontal velocity. The constant c and the moments of the distribution function are evaluated from the conservation equation in velocity space. It is found that the mean square velocity in the horizontal direction scales as O(delta(I)T), and the nontrivial third moments of the velocity distribution scale as O(delta(I)epsilon(I)T(3/2)) where epsilon(I) = (1 - e)(1/2). Here, T = [2[U2](s)/(1 - e)] is the mean square velocity of the particles.

Aerodynamics of delta wings with flaps at hypersonic speeds

Control surface effectiveness is an important parameter for any aeroplane. For a hypersonic aircraft, though the power required to operate the flaps is determined by low speed flying conditions, it is imperative to know the effect of flaps at hypersonic speeds. Hence, studies have been done on this topic by aerodynamicists for over 40 years. In spite of this, only a limited data is available in the literature on this subject. This paper discusses the experimental study of the effect of sweep on the aerodynamic characteristics of thin slab delta wings with flaps at hypersonic speeds. For the purpose of this investigation, a novel special thin six-component balance, which has a thickness of 4mm and can be housed inside wings with 8mm thickness, has been designed. The wings had a sweep of 76degrees, 70degrees and 65degrees, t/c of 0.053 and flaps with 12% of wing area and 12% of wing chord. Testing were done at Mach 8.2, Re number of 2.13 x 10(6) (based on chord), from alpha = -12degrees to 12degrees and flap angle of 20degrees, 30degrees and 40degrees. Separation lengths, measured from Schlieren pictures, clearly show that there is 'no appreciable' effect of sweep on them. Also, using a simple local flow field calculation, the separation has been identified to be transitional in nature. These features of separation reflect in the force data. Because of the small separation length, the flaps (inspite of their small size) were very effective in generating additional C-N, C-M and C-l, which increased with increase in flap angle. In general, the C-N, C-M and X-CP were unaffected by sweep for symmetric flap deflection at positive incidences and asymmetric flap case, For symmetric flap case at negative incidences, only C-N was not influenced by the sweep but C-M decreased and X-CP moved upstream as the sweep is decreased, The wing with lower sweep produces higher CA and lower (L/D)(max) for both symmetric and asymmetric flaps. The rolling moment and adverse yaw increased with decrease in sweep for asymmetric flap deflection. Newtonian theory is shown to be incapable of predicting the effect of sweep on C-l, C-n and on the incremental values of C-N, C-M and C-A. In conclusion, it can be said that a small flap is generally adequate for hypersonic aeroplanes provided they operate at altitudes where transitional and turbulent separation can be expected to occur. This would make the flaps effective and thus enable ample control authority.

Suppression of low-frequency noise in two-dimensional electron gas at degenerately doped Si:P delta layers

We report low-frequency 1/f-noise measurements of degenerately doped Si:P delta layers at 4.2 K. The noise was found to be over six orders of magnitude lower than that of bulk Si:P systems in the metallic regime and is one of the lowest values reported for doped semiconductors. The noise was nearly independent of magnetic field at low fields, indicating negligible contribution from universal conductance fluctuations. Instead, the interaction of electrons with very few active structural two-level systems may explain the observed noise magnitude.

Crystal structure and thermal and electrical properties of the perovskite solid solution Nd1-xSrxFeO3-delta (0 <= x <= 0.4)

The crystal structure, thermal expansion and electrical conductivity of strontium-doped neodymium ferrite (Nd1-xSrxFeO3-delta where 0less than or equal toxless than or equal to0.4) were investigated. All compositions had the GdFeO3-type orthorhombic perovskite structure. The lattice parameters were determined at room temperature by X-ray powder diffraction. The orthorhombic distortion decreases with increasing Sr substitution. The pseudocubic lattice parameter shows a minimum at x=0.3. The thermal expansion curves for x=0.2-0.4 displayed rapid increase in slope at higher temperatures. The electrical conductivity increased with Sr content and temperature. The calculated activation energies for electrical conduction decreased with increasing x. The electrical conductivity can be described by the small polaron hopping mechanism. The charge compensation for divalent ion on the A-site is provided by the formation of Fe4+ ions on the B site and vacancies on the oxygen sublattice. The results indicate two defect domains: for low values of x, the predominant defect is Fe4+ ions, whereas for higher values of x, oxygen vacancies dominate. (C) 2002 Elsevier Science B.V. All rights reserved.

Formation of Ce1-xPdxO2-delta solid solution in combustion-synthesized Pd/CeO2 catalyst: XRD, XPS, and EXAFS investigation

Pd/CeO2 (1 at. %) prepared by the solution-combustion method shows a higher catalytic activity for CO oxidation and NO reduction than Pd metal, PdO, and Pd dispersed over CeO2 by the conventional method. To understand the higher catalytic properties, the structure of 1 at. % Pd/CeO2 catalyst material has been investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and extended X-ray absorption fine structure (EXAFS) spectroscopy. The diffraction lines corresponding to Pd or PdO are not observed in the high-resolution XRD pattern of 1 at. % Pd/CeO2. The structure of 1 at. % Pd/CeO2 could be refined for the composition of Ce0.99Pd0.01O1.90 in the fluorite structure with 5% oxide ion vacancy. Pd(3d) peaks in the XPS in I at. % Pd/CeO2 are shifted by 3 eV indicating that Pd is in a highly ionic +2 state. EXAFS studies show the average coordination number of 3 around Pd2+ ion in the first shell of 1 at. % Pd/CeO2 at a distance of 2.02 Angstrom, instead of 4 as in PdO. The second shell at 2.72 Angstrom is due to Pd-Pd correlation which is larger than 2.69 Angstrom in PdO. The third shell at 3.31 Angstrom having 7 coordination is absent either in Pd metal or PdO, which can be attributed to -Pd2+-Ce4+- correlation. Thus, 1 at. % Pd/CeO2 forms the Ce1-xPdxO2-delta type of solid solution having -Pd2+-O-2-Ce4+- kinds of linkages.

Seismic horizontal pullout capacity of vertical anchors in sands

The problem of finding the horizontal pullout capacity of vertical anchors embedded in sands with the inclusion of pseudostatic horizontal earthquake body forces, was tackled in this note. The analysis was carried out using an upper bound limit analysis, with the consideration of two different collapse mechanisms: bilinear and composite logarithmic spiral rupture surfaces. The results are presented in nondimensional form to find the pullout resistance with changes in earthquake acceleration for different combinations of embedment ratio of the anchor (lambda), friction angle of the soil (phi), and the anchor-soil interface wall friction angle (delta). The pullout resistance decreases quite substantially with increases in the magnitude of the earthquake acceleration. For values of delta up to about 0.25-0.5phi, the bilinear and composite logarithmic spiral rupture surfaces gave almost identical answers, whereas for higher values of delta, the choice of the logarithmic spiral provides significantly smaller pullout resistance. The results compare favorably with the existing theoretical data.

Structural investigation of combustion synthesized Cu/CeO2 catalysts by EXAFS and other physical techniques: Formation of a Ce1-xCuxO2-delta solid solution

The structure and chemical environment of Cu in Cu/CeO2 catalysts synthesized by the solution combustion method have been investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), electron paramagnetic resonance (EPR) spectroscopy, X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), and extended X-ray fine structure (EXAFS) spectroscopy. High-resolution XRD studies of 3 and 5 atom % Cu/CeO2 do not show CuO lines in their respective patterns. The structure could be refined for the composition Ce1-xCuxO2-delta (x = 0.03 and 0.05; delta similar to 0.13 and 0.16) in the fluorite structure with 5-8% oxide ion vacancy. High-resolution TEM did not show CuO particles in 5 atom % Cu/CeO2. EPR as well as XPS studies confirm the presence of Cu2+ species in the CeO2 matrix. Redox potentials of Cu species in the CeO2 matrix are lower than those in CuO. EXAFS investigations of these catalysts show an average coordination number of 3 around the Cu2+ ion in the first shell at a distance of 1.96 Angstrom, indicating the O2- ion vacancy around the Cu2+ ion. The Cu-O bond length also decreases compared to that in CuO. The second and third shell around the Cu2+ ion in the catalysts are attributed to -Cu2+-O2--Cu2+ - at 2.92 Angstrom and -Cu2+-O2--Ce4+- at the distance of 3.15 Angstrom, respectively. The present results provide direct evidence for the formation of a Ce1-xCuxO2-delta type of solid solution phase having -square-Cu2+-O-Ce4+- kind of linkages.

Combustion synthesis and properties of Ce1-xPrxO2-delta red ceramic pigments

Praseodymium-doped ceria red pigments, Ce1−xPrxO2−δ, x=0–0.5 have been prepared by the thermal decomposition of the redox compound Ce1−xPrx(N2H3COO)3·3H2O as well as by the combustion of aqueous solutions containing cerous nitrate, praseodymium nitrate and oxalyl dihydrazide (ODH)/ammonium acetate. Formation of the pigment has been confirmed by its characteristic red colour and reflectance spectra which shows the reflection edge not, vert, similar690 nm corresponding to charge transfer from the ligand orbitals to the localised 4f1 of Pr4+. The particulate properties of praseodymium-doped ceria pigments obtained from the combustion of redox compounds and redox mixtures are compared.