Synthesis, X-ray structure and properties of (eta(6)-p-cymene)ruthenium(II) Schiff-base complexes of vinylpyridine and vinylimidazole ligands

Complexes of the formulation [(eta(6)-p-cymene)Ru(O-2-C6H4-CH=NC6H4-4-CH3)(L)](ClO4), where L is gamma-picoline, 4-vinylpyridine, 1-methylimidazole and 1-vinylimidazole have been prepared and characterised. The molecular structure of the vinylpyridine adduct has been determined by X-ray crystallography. The crystal belongs to the monoclinic space group P2(1) with the following cell dimensions for the C31H33CIN2O5Ru(M = 650.11): a = 10.890(2)Angstrom, b = 22.295(9)Angstrom, c = 12.930(2)Angstrom, beta = 109.30(2)degrees(3), V = 2964(l)Angstrom 3, Z = 4; D-c = 1.457g cm(-3), lambda(Mo-K alpha) = 0.7107 Angstrom; mu(Mo-K alpha)= 6.61 cm(-1); T = 293 K; R = 0.0359 (wR(2) = 0.0981) for 4819 reflections with I > 2 sigma(I). The structure shows the non-bonding nature of the double bond of the 4-vinylpyridine ligand in the complex in which the metal is bonded to the eta(6)-p-cymene, the N, O-bidentate chelating schiff-base and the unidentate N-donor pyridine ligands.

A game theoretical multiple resource interaction approach to resource allocation in an air campaign

In this paper we propose a multiple resource interaction model in a game-theoretical framework to solve resource allocation problems in theater level military campaigns. An air raid campaign using SEAD aircraft and bombers against an enemy target defended by air defense units is considered as the basic platform. Conditions for the existence of saddle point in pure strategies is proved and explicit feedback strategies are obtained for a simplified model with linear attrition function limited by resource availability. An illustrative example demonstrates the key features.

Estimation of elasticity map of soft biological tissue mimicking phantom using laser speckle contrast analysis

Scattering of coherent light from scattering particles causes phase shift to the scattered light. The interference of unscattered and scattered light causes the formation of speckles. When the scattering particles, under the influence of an ultrasound (US) pressure wave, vibrate, the phase shift fluctuates, thereby causing fluctuation in speckle intensity. We use the laser speckle contrast analysis (LSCA) to reconstruct a map of the elastic property (Young's modulus) of soft tissue-mimicking phantom. The displacement of the scatters is inversely related to the Young's modulus of the medium. The elastic properties of soft biological tissues vary, many fold with malignancy. The experimental results show that laser speckle contrast (LSC) is very sensitive to the pathological changes in a soft tissue medium. The experiments are carried out on a phantom with two cylindrical inclusions of sizes 6 mm in diameter, separated by 8 mm between them. Three samples are made. One inclusion has Young's modulus E of 40 kPa. The second inclusion has either a Young's modulus E of 20 kPa, or scattering coefficient of mu'(s), = 3.00 mm(-1) or absorption coefficient of mu(a) = 0.03 mm(-1). The optical absorption (mu(a)), reduced scattering (mu'(s)) coefficient, and the Young's modulus of the background are mu(a) = 0.01 mm(-1), mu'(s) = 1.00 mm(-1) and 12kPa, respectively. The experiments are carried out on all three phantoms. On a phantom with two inclusions of Young's modulus of 20 and 40 kPa, the measured relative speckle image contrasts are 36.55% and 63.72%, respectively. Experiments are repeated on phantoms with inclusions of mu(a) = 0.03 mm-1, E = 40 kPa and mu'(s) = 3.00 mm(-1). The results show that it is possible to detect inclusions with contrasts in optical absorption, optical scattering, and Young's modulus. Studies of the variation of laser speckle contrast with ultrasound driving force for various values of mu(a), mu'(s), and Young's modulus of the tissue mimicking medium are also carried out. (C) 2011 American Institute of Physics. doi:10.1063/1.3592352]

Simulation and experimental study on compositional evolution of Li-Co in LiCoO(2) thin films during sputter deposition

The compositional evolution in sputter deposited LiCoO(2) thin films is influenced by process parameters involved during deposition. The electrochemical performance of these films strongly depends on their microstructure, preferential orientation and stoichiometry. The transport process of sputtered Li and Co atoms from the LiCoO(2) target to the substrate, through Ar plasma in a planar magnetron configuration, was investigated based on the Monte Carlo technique. The effect of sputtering gas pressure and the substrate-target distance (d(st)) on Li/Co ratio, as well as, energy and angular distribution of sputtered atoms on the substrate were examined. Stable Li/Co ratios have been obtained at 5 Pa pressure and d(st) in the range 5 11 cm. The kinetic energy and incident angular distribution of Li and Co atoms reaching the substrate have been found to be dependent on sputtering pressure. Simulations were extended to predict compositional variations in films prepared at various process conditions. These results were compared with the composition of films determined experimentally using x-ray photoelectron spectroscopy (XPS). Li/Co ratio calculated using XPS was in moderate agreement with that of the simulated value. The measured film thickness followed the same trend as predicted by simulation. These studies are shown to be useful in understanding the complexities in multicomponent sputtering. (C) 2011 American Institute of Physics. doi:10.1063/1.3597829]

Study of the dynamics of protein folding through minimalistic models

Starting with the Levinthal paradox, a brief introduction to the protein folding problem is presented. The existing theories of protein folding, including the folding funnel scenario, are discussed. After briefly discussing different simulation studies of model proteins, we discuss our recent work on the dynamics of folding of the model HP-36 (the chicken villin headpiece) protein by using a simplified hydropathy scale. Special attention has been paid to the statics and dynamics of contact formation among the hydrophobic residues. The results obtained from this simple model appear to be surprisingly similar to several features observed in the folding of real proteins. The account concludes with a discussion of future problems.

Identification and characterization of cysteine proteinases of Trypanosoma evansi

Trypanosoma evansi is a causative agent of `surra', a common haemoprotozoan disease of livestock in India causing high morbidity and mortality in disease endemic areas. The proteinases released by live and dead trypanosomes entail immunosuppression in the infected host, which immensely contribute in disease pathogenesis. Cysteine proteinases are identified in the infectious cycle of trypanosomes such as cruzain from Trypanosoma cruzi, rhodesain or brucipain from Trypanosoma brucei rhodesiense and congopain from Trypanosoma congelense. These enzymes localised in lysosome-like organelles, flagellar pocket and on cell surface, which play a critical role in the life cycle of protozoan parasites, viz. in host invasion, nutrition and alteration of the host immune response. The paper describes the identification of cysteine proteinases of T. evansi lysate, activity profile at different pH optima and inhibition pattern using a specific inhibitor, besides the polypeptide profile of an antigen. Eight proteinases of T. evansi were identified in the molecular weight (MW) ranges of 28-170 kDa using gelatin substrate-polyacrylamide gel electrophoresis (GS-PAGE), and of these proteinases, six were cysteine proteinases, as they were inhibited by L-3-carboxy-2,3-transepoxypropionyl-lecuylamido (4-guanidino)-butane (E-64), a specific inhibitor. These proteolytic enzymes were most reactive in acidic pH between 3.0 and 5.5 in the presence of dithiothreitol and completely inactive at alkaline pH 10.0. Similarly, the GS-PAGE profile of the serum samples of rats infected with T. evansi revealed strong proteolytic activity only at the 28-kDa zone at pH 5.5, while no proteolytic activity was observed in serum samples of uninfected rats. Further, the other zones of clearance, which were evident in T. evansi antigen zymogram, could not be observed in the serum samples of rats infected with T. evansi. The polypeptide pattern of the whole cell lysate antigen revealed 12-15 polypeptide bands ranging from 28 to 81 kDa along with five predominant polypeptides bands (MW of 81, 66, 62, 55 and 45 kDa), which were immunoreactive with hyperimmune serum (HIS) and serum of experimentally infected rabbits with T. evansi infection. The immunoblot recognised antibodies in experimentally infected rabbits and against HIS as well, corresponding to the zone of clearances at lower MW ranges (28-41 kDa), which may be attributed to the potential of these proteinases in the diagnosis of T. evansi infection. Since these thiol-dependent enzymes are most active in acidic pH and considering their inhibition characteristics, these data suggest that they resemble to the mammalian lysosomal cathepsin B and L.

An ultra-stable Cu nanowire under thermo-mechanical loading: A molecular dynamic study

We report on the formation of a stable Body-Centered Heptahedral (BCH) crystalline nanobridge structure of diameter ~ 1nm under high strain rate tensile loading to a <100> Cu nanowire. Extensive Molecular Dynamics (MD) simulations are performed. Six different cross-sectional dimensions of Cu nanowires are analyzed, i.e. 0.3615 x 0.3615 nm2, 0.723 x 0.723 nm2, 1.0845 x 1.0845 nm2, 1.446 x 1.446 nm2, 1.8075 x 1.8075 nm2, and 2.169 x 2.169 nm2. The strain rates used in the present simulations are 1 x 109 s-1, 1 x 108 s-1, and 1 x 107 s-1. We have shown that the length of the nanobridge can be characterized by larger plastic strain. A large plastic deformation is an indication that the structure is highly stable. The BCH nanobridge structure also shows enhanced mechanical properties such as higher fracture toughness and higher failure strain. The effect of temperature, strain rate and size of the nanowire on the formation of BCH structure is also explained in details. We also show that the initial orientation of the nanowires play an important role on the formation of BCH crystalline structure. Results indicate that proper tailoring of temperature and strain rate during processing or in the device can lead to very long BCH nanobridge structure of Cu with enhanced mechanical properties, which may find potential application for nano-scale electronic circuits.

Analysis of Lined Ducts With Mean Flow, With Application to Dissipative Mufflers

Mufflers with at least one acoustically absorptive duct are generally called dissipative mufflers. Generally, for want of systems approach, these mufflers are characterized by transmission loss of the lined duct with overriding corrections for the terminations, mean flow, etc. In this article, it is proposed that dissipative duct should be integrated with other muffler elements, source impedance and radiation impedance, by means of transfer matrix approach. Towards this end, the transfer matrix for rectangular duct with mean flow has been derived here, for the least attenuated mode. Mean flow introduces a coupling between transverse wave numbers and axial wave number, the evaluation of which therefore calls for simultaneous solution of two or three transcendental equations. This is done by means of a Newton-Raphson iteration scheme, which is illustrated here for square ducts lined with porous ceramic tiles.

The generalized Onsager model for the secondary flow in a high-speed rotating cylinder

The generalizations of the Onsager model for the radial boundary layer and the Carrier-Maslen model for the end-cap axial boundary layer in a high-speed rotating cylinder are formulated for studying the secondary gas flow due to wall heating and due to insertion of mass, momentum and energy into the cylinder. The generalizations have wider applicability than the original Onsager and Carrier-Maslen models, because they are not restricted to the limit A >> 1, though they are restricted to the limit R e >> 1 and a high-aspect-ratio cylinder whose length/diameter ratio is large. Here, the stratification parameter A = root m Omega(2)R(2)/2k(B)T). This parameter A is the ratio of the peripheral speed, Omega R, to the most probable molecular speed, root 2k(B)T/m, the Reynolds number Re = rho w Omega R(2)/mu, where m is the molecular mass, Omega and R are the rotational speed and radius of the cylinder, k(B) is the Boltzmann constant, T is the gas temperature, rho(w) is the gas density at wall, and mu is the gas viscosity. In the case of wall forcing, analytical solutions are obtained for the sixth-order generalized Onsager equations for the master potential, and for the fourth-order generalized Carrier-Maslen equation for the velocity potential. For the case of mass/momentum/energy insertion into the flow, the separation-of-variables procedure is used, and the appropriate homogeneous boundary conditions are specified so that the linear operators in the axial and radial directions are self-adjoint. The discrete eigenvalues and eigenfunctions of the linear operators (sixth-order and second-order in the radial and axial directions for the Onsager equation, and fourth-order and second-order in the axial and radial directions for the Carrier-Maslen equation) are determined. These solutions are compared with direct simulation Monte Carlo (DSMC) simulations. The comparison reveals that the boundary conditions in the simulations and analysis have to be matched with care. The commonly used `diffuse reflection' boundary conditions at solid walls in DSMC simulations result in a non-zero slip velocity as well as a `temperature slip' (gas temperature at the wall is different from wall temperature). These have to be incorporated in the analysis in order to make quantitative predictions. In the case of mass/momentum/energy sources within the flow, it is necessary to ensure that the homogeneous boundary conditions are accurately satisfied in the simulations. When these precautions are taken, there is excellent agreement between analysis and simulations, to within 10 %, even when the stratification parameter is as low as 0.707, the Reynolds number is as low as 100 and the aspect ratio (length/diameter) of the cylinder is as low as 2, and the secondary flow velocity is as high as 0.2 times the maximum base flow velocity. The predictions of the generalized models are also significantly better than those of the original Onsager and Carrier-Maslen models, which are restricted to thin boundary layers in the limit of high stratification parameter.

Simulation and experimental study on compositional evolution of Li-Co in LiCoO2 thin films during sputter deposition

The compositional evolution in sputter deposited LiCoO2 thin films is influenced by process parameters involved during deposition. The electrochemical performance of these films strongly depends on their microstructure, preferential orientation and stoichiometry. The transport process of sputtered Li and Co atoms from the LiCoO2 target to the substrate, through Ar plasma in a planar magnetron configuration, was investigated based on the Monte Carlo technique. The effect of sputtering gas pressure and the substrate-target distance (dst) on Li/Co ratio, as well as, energy and angular distribution of sputtered atoms on the substrate were examined. Stable Li/Co ratios have been obtained at 5 Pa pressure and dst in the range 5−11 cm. The kinetic energy and incident angular distribution of Li and Co atoms reaching the substrate have been found to be dependent on sputtering pressure. Simulations were extended to predict compositional variations in films prepared at various process conditions. These results were compared with the composition of films determined experimentally using x-ray photoelectron spectroscopy (XPS). Li/Co ratio calculated using XPS was in moderate agreement with that of the simulated value. The measured film thickness followed the same trend as predicted by simulation. These studies are shown to be useful in understanding the complexities in multicomponent sputtering.

On the magnetization reversal of the oxide-based exchange spring magnet

The role of the soft phase (Ni0.8Zn0.2Fe2O4) on the magnetization reversal and coercivity mechanism of the Ni0.8Zn0.2Fe2O4/BaFe12O19 nanocomposite has been investigated. The presence of the interacting field and the disorder in the nanocomposite has been confirmed by the variation of Jr/Jr(∞) vs Jd/Jr(∞) and the irreversible magnetization. To understand the relative strength of the pinning and the nucleation, the magnetic viscosity measurement has been done and the thermal activation volume has been estimated. From the Barbier plot and the activation volume measurement, the dominant mechanism governing the magnetization reversal process has been proposed.

Band alignment studies in InN/p-Si(100) heterojunctions by x-ray photoelectron spectroscopy

The band offsets in InN/p-Si heterojunctions are determined by high resolution x-ray photoemission spectroscopy. The valence band of InN is found to be 1.39 eV below that of Si. Given the bandgap of 0.7 eV for InN, a type-III heterojunction with a conduction band offset of 1.81 eV was found. Agreement between the simulated and experimental data obtained from the heterojunction spectra was found to be excellent, establishing that the method of determination was accurate. The charge neutrality level (CNL) model provided a reasonable description of the band alignment of the InN/p-Si interface and a change in the interface dipole by 0.06 eV was observed for InN/p-Si interface.