Aqueous channels within apolar peptide aggregates. Solvated helix of Boc-Aib-Ala-Leu-Aib-Ala-Leu-Aib- -Ala-Leu-Aib-OMe. H2O.CH3OH

Although the peptide Boc-Aibl-Ala2-Leu3- Aib4-Alas Leu'-Aib7-Ala8-Leu9-Aib'0-OMe [with a t-butoxycarbonyl(Boc) blocking group at the amino terminus, a methyl ester (OMe) at the carboxyl terminus, and four a-aminoisobutyric (Aib) residues] has a 3-fold repeat of residues, the helix formed by the peptide backbone is irregular. The carboxyl-terminal half assumes an at-helical form with torsion angles ) and r of approximately -60° and -45°, respectively, whereas the amino-terminal half is distorted by an insertion of a water molecule between the amide nitrogen of Ala5 [N(5)] and the carbonyl oxygen of Ala2 [0(2)]. The water molecule W(1) acts as a bridge by forming hydrogen bonds N(5).W(1) (2.93 A) and W(1)---0(2) (2.86 A). The distortion of the helix exposes the carbonyl oxygens of Aib' and Aib4 to the outside environment, with the consequence that the helix assumes an amphiphilic character despite having all apolar residues. Neighboring helices in the crystal run in antiparallel directions. On one side of a helix there are only hydrophobic contacts with efficient interdigitation of leucine side chains with those from the neighboring helix. On the other side of the helix there are hydrogen bonds between protruding carbonyl oxygens and four water molecules that separate two neighboring helices. Along the helix axis the helices bind head-to-tail with a direct hydrogen bond N(2)-0(9) (3.00 A). Crystals grown from methanol/water solution are in space group P2, with a = 15.778 ± 0.004 A, b = 11.228 ± 0.002 A, c = 18.415 ± 0.003 A, = 102.10 ± 0.02ur and two formula units per cell for C49HON1003 2H2OCH3OH. The overall agreement factorR is 7.5% for 3394 reflections observed with intensities >3a(F), and the resolution is 0.90 A.

Bayesian Analysis of a Superimposed Renewal Process

Stochastic behavior of an aero-engine failure/repair process has been analyzed from a Bayesian perspective. Number of failures/repairs in the component-sockets of this multi-component system are assumed to follow independent renewal processes with Weibull inter-arrival times. Based on the field failure/repair data of a large number of such engines and independent Gamma priors on the scale parameters and log-concave priors on the shape parameters, an exact method of sampling from the resulting posterior distributions of the parameters has been proposed. These generated parameter values are next utilised in obtaining the posteriors of the expected number of system repairs, system failure rate, and the conditional intensity function, which are computed using a recursive formula.

Metal-Insulator Transition in the Hubbard Model on a Triangular Lattice

We discuss the results of an extensive mean-field investigation of the half-filled Hubbard model on a triangular lattice at zero temperature. At intermediate U we find a first-order metal-insulator transition from an incommensurate spiral magnetic metal to a semiconducting state with a commensurate linear spin density wave ordering stabilized by the competition between the kinetic energy and the frustrated nature of the magnetic interaction. At large U the ground state is that of a classical triangular antiferromagnet within our approximation. In the incommensurate spiral metallic phase the Fermi surface has parts in which the wave function renormalization Z is extremely small. The evolution of the Fermi surface and the broadening of the quasi-particle band along with the variation of the plasma frequency and a charge stiffness constant with U/t are discussed.

Reactivity Of Pph3 Toward Ruiiruiiicl(O2car)4 - Syntheses, Molecular-Structures, And Spectroscopic And Electrochemical Properties Of Ruiiruiii(Oh2)Cl(Mecn)(O2car)4(Pph3)2 And Ruii2(Oh2)(Mecn)2(O2car)4(Pph3)2

By the reaction of Ru2Cl(O2CAr)4 (1) and PPh3 in MeCN-H2O the diruthenium(II,III) and diruthenium(II) compounds of the type Ru2(OH2)Cl(MeCN)(O2CAr)4(PPh3)2 (2) and Ru2(OH2)(MeCN)2(O2CAr)4(PPh3)2 (3) were prepared and characterized by analytical, spectral, and electrochemical data (Ar is an aryl group, C6H4-p-X; X = H, OMe, Me, Cl, NO2). The molecular structure of Ru2(OH2)Cl(MeCN)(O2CC6H4-p-OMe)4(PPh3)2 was determined by X-ray crystallography. Crystal data are as follows: triclinic, P1BAR, a = 13.538 (5) angstrom, b = 15.650 (4) angstrom, c = 18.287 (7) angstrom, alpha = 101.39 (3)-degrees, beta = 105.99 (4)-degrees, gamma = 97.94 (3)-degrees, V = 3574 angstrom 3, Z = 2. The molecule is asymmetric, and the two ruthenium centers are clearly distinguishable. The Ru(III)-Ru(II), Ru(III)-(mu-OH2), and Ru(II)-(mu-OH2) distances and the Ru-(mu-OH2)-Ru angle in [{Ru(III)Cl(eta-1-O2CC6H4-p-OMe)(PPh3)}(mu-OH2)(mu-O2CC6H4-p-OMe)2{Ru(II)(MeCN)(eta-1-O2CC6H4-p-OMe)(PPh3)}] are 3.604 (1), 2.127 (8), and 2.141 (10) angstrom and 115.2 (5)-degrees, respectively. The compounds are paramagnetic and exhibit axial EPR spectra in the polycrystalline form. An intervalence transfer (IT) transition is observed in the range 900-960 nm in chloroform in these class II type trapped mixed-valence species 2. Compound 2 displays metal-centered one-electron reduction and oxidation processes near -0.4 and +0.6 V (vs SCE), respectively in CH2Cl2-TBAP. Compound 2 is unstable in solution phase and disproportionates to (mu-aquo)diruthenium(II) and (mu-oxo)diruthenium(III) complexes. The mechanistic aspects of the core conversion are discussed. The molecular structure of a diruthenium(II) compound, Ru2(OH2)(MeCN)2(O2CC6H4-p-NO2)4(PPh3)2.1.5CH2Cl2, was obtained by X-ray crystallography. The compound crystallizes in the space group P2(1)/c with a = 23.472 (6) angstrom, b = 14.303 (3) angstrom, c = 23.256 (7) angstrom, beta = 101.69 (2)-degrees, V = 7645 angstrom 3, and Z = 4. The Ru(II)-Ru(II) and two Ru(II)-(mu-OH2) distances and the Ru(II)-(mu-OH2)-Ru(II) angle in [{(PPh3)-(MeCN)(eta-1-O2CC6H4-p-NO2)Ru}2(mu-OH2)(mu-O2CC6H4-p-NO2)2] are 3.712 (1), 2.173 (9), and 2.162 (9) angstrom and 117.8 (4)-degrees, respectively. In both diruthenium(II,III) and diruthenium(II) compounds, each metal center has three facial ligands of varying pi-acidity and the aquo bridges are strongly hydrogen bonded with the eta-1-carboxylato facial ligands. The diruthenium(II) compounds are diamagnetic and exhibit characteristic H-1 NMR spectra in CDCl3. These compounds display two metal-centered one-electron oxidations near +0.3 and +1.0 V (vs SCE) in CH2Cl2-TBAP. The overall reaction between 1 and PPh3 in MeCN-H2O through the intermediacy of 2 is of the disproportionation type. The significant role of facial as well as bridging ligands in stabilizing the core structures is observed from electrochemical studies.

New twelve node serendipity quadrilateral plate bending element based on Mindlin-Reissner theory using Integrated Force Method

The Integrated Force Method (IFM) is a novel matrix formulation developed for analyzing the civil, mechanical and aerospace engineering structures. In this method all independent/internal forces are treated as unknown variables which are calculated by simultaneously imposing equations of equilibrium and compatibility conditions. This paper presents a new 12-node serendipity quadrilateral plate bending element MQP12 for the analysis of thin and thick plate problems using IFM. The Mindlin-Reissner plate theory has been employed in the formulation which accounts the effect of shear deformation. The performance of this new element with respect to accuracy and convergence is studied by analyzing many standard benchmark plate bending problems. The results of the new element MQP12 are compared with those of displacement-based 12-node plate bending elements available in the literature. The results are also compared with exact solutions. The new element MQP12 is free from shear locking and performs excellent for both thin and moderately thick plate bending situations.

V2o5-Based Hydrocarbon Sensors

V2O5 supported on ZrO2 is found to be an excellent sensor for n-propane-butane mixtures at 625 K; in-situ X-ray diffraction studies show that V2O5 is reduced to VO2 with a metastable monoclinic structure on contact with the hydrocarbons and is oxidised back to the parent oxide on exposure to air.

A Multi frequency study of Radio Intensity Variations For Active Galactic Nuclei of Different Optical Classes

A study of radio intensity variations at seven frequencies in the range 0.3 to 90 GHz for compact extragalactic radio sources classified as BL Lacs and high- and low-optical polarization quasars (HPQs and LPQs) is presented. This include the results of flux-density monitoring of 33 compact sources for three years at 327 MHz with the Ooty Synthesis Radio Telescope. The degrees of 'short-term' (tau less than about 1 yr) variability for the three optical types are found to be indistinguishable at low frequencies (less than 1 GHz), pointing to an extrinsic origin for the low-frequency variability. At high frequencies, a distinct dependence on optical type is present, the variability increasing from LPQs, through HPQs to BL Lacs. This trend persists even when only sources with ultra-flat radio spectra (alpha greater than -0.2) are considered. Implications of this for the phenomenon of high-frequency variability and the proposed unification schemes for different optical types of active galactic nuclei are discussed.

Non-Newtonian boundary layers on a moving cylinder

The analysis of steady laminar forced convection boundary layer of power-law non-Newtonian fluids on a continuously moving cylinder with the surface maintained at a uniform temperature or uniform heat flux is presented. Of interest were the effects of power-law viscosity index, transverse curvature, generalized Prandtl number and streamwise coordinate on the local Nusselt number as well as on the velocity and temperature profiles. The two thermal boundary conditions yield quite similar results. Comparison of the calculated results with available series expansion solutions for a Newtonian fluid shows a very good performance of the present numerical procedure.

Relaxation system based sub-grid scale modelling for large eddy simulation of Burgers' equation

An implicit sub-grid scale model for large eddy simulation is presented by utilising the concept of a relaxation system for one dimensional Burgers' equation in a novel way. The Burgers' equation is solved for three different unsteady flow situations by varying the ratio of relaxation parameter (epsilon) to time step. The coarse mesh results obtained with a relaxation scheme are compared with the filtered DNS solution of the same problem on a fine mesh using a fourth-order CWENO discretisation in space and third-order TVD Runge-Kutta discretisation in time. The numerical solutions obtained through the relaxation system have the same order of accuracy in space and time and they closely match with the filtered DNS solutions.

Nonvaporable Getter Application in Cryogenic Systems

The application of non-evaporable Zr-V-Fe getters to enhance and maintain the vacuum of cryogenic systems have been studied. It has been shown that the pressur erise rate of the insulation space of these systems are significantly reduced by the getter activation. The gettering action is substantial even at abient temperature for many gases including hydrogen which can not be cryosorbed at LN2 temperatures. The getter can be activated several times and they can act as in-situ pumps for cryogenic systems, especially for field units.

Fracture Properties of Concrete-Concrete Interfaces Using Digital Image Correlation

The mode I and mode II fracture toughness and the critical strain energy release rate for different concrete-concrete jointed interfaces are experimentally determined using the Digital Image Correlation technique. Concrete beams having different compressive strength materials on either side of a centrally placed vertical interface are prepared and tested under three-point bending in a closed loop servo-controlled testing machine under crack mouth opening displacement control. Digital images are captured before loading (undeformed state) and at different instances of loading. These images are analyzed using correlation techniques to compute the surface displacements, strain components, crack opening and sliding displacements, load-point displacement, crack length and crack tip location. It is seen that the CMOD and vertical load-point displacement computed using DIC analysis matches well with those measured experimentally.

An examination of the BEBO model with the results of ab initio calculations of a reaction series

The BEBO (bond energy-bond order) model of Johnston and Parr is examined with the results of ab initio MO calculations on a series of metathetic reactions which involve hydrogen transfer. Energies are calculated at the 6-31G**/PMP2 = full//6-31G** level while the bond orders are estimated using the 6-31G** basis set with the geometry optimisation at the single configuration unrestricted Hartree-Fock frame. Our analysis reveals that the bond-order exponent in the BEBO theory is greater than unity for the reaction series and the entropy term becomes implicitly present in the BEBO model.