Dicopper(II) complexes showing DNA hydrolase activity and monomeric adduct formation with bis(4-nitrophenyl)phosphate

Ferromagnetic dicopper(II) complexes [Cu(2)(mu-O(2)CCH(3))(mu-OH)(L)(2)(mu-L(1))](PF(6))(2), where L = 1,10-phenanthroline (phen), L(1) = H(2)O in 1 and L = dipyrido[3,2-d:2',3'-f]quinoxaline (dpq), L(1) = CH(3)CN in 2, are prepared and structurally characterized. Crystals of 1 and 2 belong to the monoclinic space group of P2(1)/n and P2(1)/m, respectively. The copper(II) centers display distorted square-pyramidal geometry having a phenanthroline base and two oxygen atoms of the bridging hydroxo and acetate group in the basal plane. The fifth coordination site has weak axially bound bridging solvent molecule H(2)O in 1 and CH(3)CN in 2. The Cu center dot center dot center dot Cu distances are 3.034 and 3.046 angstrom in 1 and 2, respectively. The complexes show efficient hydrolytic cleavage of supercoiled pUC19 DNA as evidenced from the mechanistic studies that include T4 DNA ligase experiments. The binuclear complexes form monomeric copper(II) adducts [Cu(L)(2)(BNPP)](PF(6)) (L = phen, 3; dpq, 4) with bis(4-nitrophenyl)phosphate (BNPP) as a model phosphodiester. The crystal structures of 3 and 4 reveal distorted trigonal bipyramidal geometry in which BNPP binds through the oxygen atom of the phosphate. The kinetic data of the DNA cleavage reactions of the binuclear complexes under pseudo- and true-Michaelis-Menten conditions indicate remarkable enhancement in the DNA hydrolysis rate in comparison to the control data. (C) 2011 Elsevier B.V. All rights reserved.

Theoretical determination of HI vertical scale heights in the dwarf galaxies DDO 154, Ho II, IC 2574 and NGC 2366

In this paper, we model dwarf galaxies as a two-component system of gravitationally coupled stars and atomic hydrogen gas in the external force field of a pseudo-isothermal dark matter halo, and numerically obtain the radial distribution of HI vertical scale heights. This is done for a group of four dwarf galaxies (DDO 154, Ho II, IC 2574 and NGC 2366) for which most necessary input parameters are available from observations. The formulation of the equations takes into account the rising rotation curves generally observed in dwarf galaxies. The inclusion of self-gravity of the gas into the model at par with that of the stars results in scale heights that are smaller than what was obtained by previous authors. This is important as the gas scale height is often used for deriving other physical quantities. The inclusion of gas self-gravity is particularly relevant in the case of dwarf galaxies where the gas cannot be considered a minor perturbation to the mass distribution of the stars. We find that three out of four galaxies studied show a flaring of their HI discs with increasing radius, by a factor of a few within several disc scale lengths. The fourth galaxy has a thick HI disc throughout. This flaring arises as a result of the gas velocity dispersion remaining constant or decreasing only slightly while the disc mass distribution declines exponentially as a function of radius.

Modeling of nonreacting and reacting turbulent spray jets using a fully stochastic separated flow approach

Numerical modeling of several turbulent nonreacting and reacting spray jets is carried out using a fully stochastic separated flow (FSSF) approach. As is widely used, the carrier-phase is considered in an Eulerian framework, while the dispersed phase is tracked in a Lagrangian framework following the stochastic separated flow (SSF) model. Various interactions between the two phases are taken into account by means of two-way coupling. Spray evaporation is described using a thermal model with an infinite conductivity in the liquid phase. The gas-phase turbulence terms are closed using the k-epsilon model. A novel mixture fraction based approach is used to stochastically model the fluctuating temperature and composition in the gas phase and these are then used to refine the estimates of the heat and mass transfer rates between the droplets and the surrounding gas-phase. In classical SSF (CSSF) methods, stochastic fluctuations of only the gas-phase velocity are modeled. Successful implementation of the FSSF approach to turbulent nonreacting and reacting spray jets is demonstrated. Results are compared against experimental measurements as well as with predictions using the CSSF approach for both nonreacting and reacting spray jets. The FSSF approach shows little difference from the CSSF predictions for nonreacting spray jets but differences are significant for reacting spray jets. In general, the FSSF approach gives good predictions of the flame length and structure but further improvements in modeling may be needed to improve the accuracy of some details of the Predictions. (C) 2011 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Estimation of missing data using windowed linear prediction in laterally truncated projection & in cone beam CT

In this paper, we address the reconstruction problem from laterally truncated helical cone-beam projections. The reconstruction problem from lateral truncation, though similar to that of interior radon problem, is slightly different from it as well as the local (lambda) tomography and pseudo-local tomography in the sense that we aim to reconstruct the entire object being scanned from a region-of-interest (ROI) scan data. The method proposed in this paper is a projection data completion approach followed by the use of any standard accurate FBP type reconstruction algorithm. In particular, we explore a windowed linear prediction (WLP) approach for data completion and compare the quality of reconstruction with the linear prediction (LP) technique proposed earlier.

Filtered density function for large eddy simulation of turbulent reacting flows

A methodology termed the “filtered density function” (FDF) is developed and implemented for large eddy simulation (LES) of chemically reacting turbulent flows. In this methodology, the effects of the unresolved scalar fluctuations are taken into account by considering the probability density function (PDF) of subgrid scale (SGS) scalar quantities. A transport equation is derived for the FDF in which the effect of chemical reactions appears in a closed form. The influences of scalar mixing and convection within the subgrid are modeled. The FDF transport equation is solved numerically via a Lagrangian Monte Carlo scheme in which the solutions of the equivalent stochastic differential equations (SDEs) are obtained. These solutions preserve the Itô-Gikhman nature of the SDEs. The consistency of the FDF approach, the convergence of its Monte Carlo solution and the performance of the closures employed in the FDF transport equation are assessed by comparisons with results obtained by direct numerical simulation (DNS) and by conventional LES procedures in which the first two SGS scalar moments are obtained by a finite difference method (LES-FD). These comparative assessments are conducted by implementations of all three schemes (FDF, DNS and LES-FD) in a temporally developing mixing layer and a spatially developing planar jet under both non-reacting and reacting conditions. In non-reacting flows, the Monte Carlo solution of the FDF yields results similar to those via LES-FD. The advantage of the FDF is demonstrated by its use in reacting flows. In the absence of a closure for the SGS scalar fluctuations, the LES-FD results are significantly different from those based on DNS. The FDF results show a much closer agreement with filtered DNS results. © 1998 American Institute of Physics.

Dynamic Multiscaling in Two-Dimensional Fluid Turbulence

We obtain, by extensive direct numerical simulations, time-dependent and equal-time structure functions for the vorticity, in both quasi-Lagrangian and Eulerian frames, for the direct-cascade regime in two-dimensional fluid turbulence with air-drag-induced friction. We show that different ways of extracting time scales from these time-dependent structure functions lead to different dynamic-multiscaling exponents, which are related to equal-time multiscaling exponents by different classes of bridge relations; for a representative value of the friction we verify that, given our error bars, these bridge relations hold.

Alloy oxide equilibria in the system Ca Al O at 1373 K

The tie lines delineating equilibria between different oxides of the Ca-Al-O system and liquid Ca-Al alloy has been determined at 1373 K. Equilibration of the alloy with two adjacent oxide phases in the CaO-Al2O3 pseudo-binary system was established in a closed cell made of iron. Equilibrium oxide phases were confirmed by x-ray analysis and alloy compositions were determined by chemical analysis. The compound 12CaO.7Al2O3 Ca12Al14O33 was found to be a stable phase in equilibrium with calcium alloys. The experimental diagram is consistent with that calculated from the free energies of formation of the oxide phases and activities in liquid Ca-Al alloys at 1373 K reported in the literature.

A thermodynamic study of liquid Cu-Cr alloys and metastable liquid immiscibility

he thermodynamic acitivity of chromium in liquid Cu-Cr alloys is measured in the temperature range from 1473 to 1873 K using the solid state cell: Pt, W, Cr + Cr2O3 |(Y2O3) ThO2|Cu - Cr + Cr2O3, Pt The activity of copper and the Gibbs energy of mixing of the liquid alloy are derived. Activities exhibit large positive deviations from Raoult's law. The mixing properties can be represented by a pseudo-subregular solution model in which the excess entropy has the same type of functional dependence on composition as the enthalpy of mixing: ΔGE = XCr(1 - XCr)[60880 - 18750 XCr)-- T(16.25 - 7.55 XCr)]J mol-1 Pure liquid Cu and Cr are taken as the reference states. The results predict a liquid-liquid metastable miscibility gap, with TC = 1787 (±3) K and XCr = 0.436 (±0.02), lying below the liquidus. The results obtained in this study are in general agreement with experimental information reported in the literature, but provide further refinement of the thermodynamic parameters.

Gibbs energy of formation of CaCu3Ti4O12 and phase relations in the system CaO-CUO/CU2O-TiO2

he standard Gibbs energy of formation of CaCu3Ti4O12 (CCTO) from CaTiO3, CuO and TiO2 has been determined as a function of temperature from 925 to 1350 K using a solid-state electrochemical cell with yttria-stabilized zirconia as the solid electrolyte. Combining this result with information in the literature on CaTiO3, the standard Gibbs energy of formation of CCTO from its component binary oxides, CaO, CuO and TiO2, has been obtained: View the MathML source (CaCu3Ti4O12)/J mol−1 (±600) = −125231 + 6.57 (T/K). The oxygen chemical potential corresponding to the reduction of CCTO to CaTiO3, TiO2 and Cu2O has been calculated from the electrochemical measurements as a function of temperature and compared on an Ellingham diagram with those for the reduction of CuO to Cu2O and Cu2O to Cu. The oxygen partial pressures corresponding to the reduction reactions at any chosen temperature can be read using the nomograms provided on either side of the diagram. The effect of the oxygen partial pressure on phase relations in the pseudo-ternary system CaO–CuO/Cu2O–TiO2 at 1273 K has been evaluated. The phase diagrams allow identification of secondary phases that may form during the synthesis of the CCTO under equilibrium conditions. The secondary phases may have a significant effect on the extrinsic component of the colossal dielectric response of CCTO.

Thermodynamic properties of calcium titanates: CaTiO3, Ca4Ti3O10, and Ca3Ti2O7

The chemical potentials of CaO in two-phase fields (TiO2 + CaTiO3), (CaTiO3 + Ca4Ti3O10), and (Ca4Ti3O10 + Ca3Ti2O7) of the pseudo-binary system (CaO + TiO2) have been measured in the temperature range (900 to 1250) K, relative to pure CaO as the reference state, using solid-state galvanic cells incorporating single crystal CaF2 as the solid electrolyte. The cells were operated under pure oxygen at ambient pressure. The standard Gibbs free energies of formation of calcium titanates, CaTiO3, Ca4Ti3O10, and Ca3Ti2O7, from their component binary oxides were derived from the reversible e.m.f.s. The results can be summarised by the following equations: CaO(solid) + TiO2(solid) → CaTiO3(solid), ΔG° ± 85/(J · mol−1) = −80,140 − 6.302(T/K); 4CaO(solid) + 3TiO2(solid) → Ca4Ti3O10(solid), ΔG° ± 275/(J · mol−1) = −243,473 − 25.758(T/K); 3CaO(solid) + 2TiO2(solid) → Ca3Ti2O7(solid), ΔG° ± 185/(J · mol−1) = −164,217 − 16.838(T/K). The reference state for solid TiO2 is the rutile form. The results of this study are in good agreement with thermodynamic data for CaTiO3 reported in the literature. For Ca4Ti3O10 Gibbs free energy of formation obtained in this study differs significantly from that reported by Taylor and Schmalzried at T = 873 K. For Ca3Ti2O7 experimental measurements are not available in the literature for direct comparison with the results obtained in this study. Nevertheless, the standard entropy for Ca3Ti2O7 at T = 298.15 K estimated from the results of this study using the Neumann–Koop rule is in fair agreement with the value obtained from low-temperature heat capacity measurements.

Synthesis, Reactivity Studies, Structural Aspects, and Solution Behavior of Half Sandwich Ruthenium(II) N,N `,N `'-Triarylguanidinate Complexes

[(eta(6)-C(10)H(14))RuCl(mu-Cl)](2) (eta(6)-C(10)H(14) = eta(6)-p-cymene) was subjected to a bridge-splitting reaction with N,N',N `'-triarylguanidines, (ArNH)(2)C=NAr, in toluene at ambient temperature to afford [(eta(6)-C(10)H(14))RuCl{kappa(2)(N,N')((ArN)(2)C-N(H)Ar)}] (Ar = C(6)H(4)Me-4 (1), C(6)H(4)(OMe)-2 (2), C(6)H(4)Me-2 (3), and C(6)H(3)Me(2)-2,4 (4)) in high yield with a view aimed at understanding the influence of substituent(s) on the aryl rings of the guanidine upon the solid-state structure, solution behavior, and reactivity pattern of the products. Complexes 1-3 upon reaction with NaN(3) in ethanol at ambient temperature afforded [(eta(6)-C(10)H(14))RuN(3){kappa(2)(N,N')((ArN)(2)C-N(H)Ar)}] (Ar = C(6)H(4)Me-4 (5), C(6)H(4)(OMe)-2 (6), and C(6)H(4)Me-2 (7)) in high yield. [3 + 2] cycloaddition reaction of 5-7 with RO(O)C-C C-C(O)OR (R = Et (DEAD) and Me (DMAD)) (diethylacetylenedicarboxylate, DEAD; dimethylacetylenedicarboxylate, DMAD) in CH(2)Cl(2) at ambient temperature afforded [(eta(6)-C(10)H(14))Ru{N(3)C(2)(C(O)OR)(2)}{kappa(2)(N,N')((ArN)(2) C-N(H)Ar)}center dot xH(2)O (x = 1, R = Et, Ar = C(6)H(4)Me-4 (8 center dot H(2)O); x = 0, R = Me, Ar = C(6)H(4)(OMe)-2 (9), and C(6)H(4)Me-2 (10)) in moderate yield. The molecular structures of 1-6, 8 center dot H(2)O, and 10 were determined by single crystal X-ray diffraction data. The ruthenium atom in the aforementioned complexes revealed pseudo octahedral ``three legged piano stool'' geometry. The guanidinate ligand in 2, 3, and 6 revealed syn-syn conformation and that in 4, and 10 revealed syn-anti conformation, and the conformational difference was rationalized on the basis of subtle differences in the stereochemistry of the coordinated nitrogen atoms caused by the aryl moiety in 3 and 4 or steric overload caused by the substituents around the ruthenium atom in 10. The bonding pattern of the CN(3) unit of the guanidinate ligand in the new complexes was explained by invoking n-pi conjugation involving the interaction of the NHAr/N(coord)Ar lone pair with C=N pi* orbital of the imine unit. Complexes 1, 2, 5, 6, 8 center dot H(2)O, and 9 were shown to exist as a single isomer in solution as revealed by NMR data, and this was ascribed to a fast C-N(H)Ar bond rotation caused by a less bulky aryl moiety in these complexes. In contrast, 3 and 10 were shown to exist as a mixture of three and five isomers in about 1:1:1 and 1.0:1.2:2:7:3.5:6.9 ratios, respectively in solution as revealed by a VT (1)H NMR, (1)H-(1)H COSY in conjunction with DEPT-90 (13)C NMR data measured at 233 K in the case of 3. The multiple number of isomers in solution was ascribed to the restricted C-N(H)(o-tolyl) bond rotation caused by the bulky o-tolyl substituent in 3 or the aforementioned restricted C-NH(o-tolyl) bond rotation as well as the restricted ruthenium-arene(centroid) bond rotation caused by the substituents around the ruthenium atom in 10.

Appraisal of Bishop's method of slope stability analysis

The stability of slopes is a major problem in geotechnical engineering. Of the methods available for the analysis of soil slopes such as limit equilibrium methods, limit analysis and numerical methods such as FEM and FDM, limit equilibrium methods are popular and generally used, owing to their simplicity in formulation and in evaluating the overall factor of safety of slope. However limit equilibrium methods possess certain disadvantages. They do not consider whether the slope is an embankment or natural slope or an excavation and ignore the effect of incremental construction, initial stress, stress strain behavior etc. In the work reported in this paper, a comparative study of actual state of stress and actual factor of safety and Bishop's factor of safety is performed. The actual factor of safety is obtained by consideration of contours of mobilised shear strains. Using Bishop's method of slices, the critical slip surfaces of a number of soil slopes with different geometries are determined and both the factors of safety are obtained. The actual normal stresses and shear stresses are determined from finite difference formulation using FLAG (Fast Lagrangian Analysis of Continuaa) with Mohr-Coulomb model. The comparative study is performed in terms of parameter lambda(c phi) (= gamma H tan phi/c). I is shown that actual factor of safety is higher than Bishop's factor of safety depending on slope angle and lambda(c phi).

Experimental and Theoretical Studies of Unusual Four-Membered Metallacycles from Reactions of Group 4 Metallocene Bis(trimethylsilyl)-acetylene Complexes with the Sulfurdiimide Me3SiN=S=NSiMe3

The use of the sulfurdiimide RN=S=NR' (R = R' = SiMe3, 3) in reactions with group 4 metallocene bis(trimethylsilyl)-acetylene complexes of the type [Cp2M(L (eta(2)-Me3Si-C2SiMe3)] (1: M = Ti, no L; 2: M = Zr, L = pyridine) has led to the formation of four-membered metallacycles 4M containing the group 4 metal, nitrogen and sulfur. DFT calculations performed on compound 4Ti indicate that this complex is best described as a sigma-complex with cyclic delocalisation of the ring electrons. Moreover, pseudo-Jahn-Teller distortion plays a significant role in stabilising this complex.

Electrochemical, phosphate hydrolysis, DNA binding and DNA cleavage properties of new polyaza macrobicyclic dinickel(II) complexes

A new class of macrobicyclic dinickel(II) complexes Ni2L1,2 B](ClO4)(4) (1-6), where L-1,L-2 are polyaza macrobicyclic binucleating ligands, and B is a N,N-donor heterocyclic base (viz. 2,2'-bipyridine (bipy) and 1,10-phenanthroline (phen)) are synthesized and characterized. The redox, catalytic, DNA binding and DNA cleavage properties were studied. They exhibit two irreversible waves in the cathodic region around E-pc = -0.95 V and E-pa = -0.85 V vs. Ag/Ag+ in CH3CN-0.1 M TBAP, respectively. The first order rate constants for the hydrolysis of 4-nitrophenylphosphate to 4-nitrophenolate by the dinickel(II) complexes 1-6 are in the range from 3.36 x 10(-5) to 10.83 x 10(-5) Ms-1. The complexes 3 and 6 show good binding propensity to calf thymus DNA giving binding constant values (K-b) in the range from 3.08 x 10(5) to 5.37 x 10(5) M-1. The binding site sizes and viscosity data suggest the DNA intercalative and/or groove binding nature of the complexes. The complexes display significant hydrolytic cleavage of supercoiled pBR322DNA at pH 7.2 and 37 degrees C. The hydrolytic cleavage of DNA by the complexes is supported by the evidence from free radical quenching and T4 ligase ligation. The pseudo Michaelis-Menten kinetic parameters k(cat) = 5.44 x 10(-2) h(-1) and K-M = 6.23 x 10(-3) M for complex 3 were obtained. Complex 3 also shows an enormous enhancement of the cleavage rate, of 1.5 x 10(6), in comparison to the uncatalysed hydrolysis rate (k = 3.6 x 10(-8) h(-1)) of ds-DNA.

ENTANGLEMENT IN A 3-SPIN HEISENBERG-XY CHAIN WITH NEAREST-NEIGHBOR INTERACTIONS, SIMULATED IN AN NMR QUANTUM SIMULATOR

The evolution of entanglement in a 3-spin chain with nearest-neighbor Heisenberg-XY interactions for different initial states is investigated here. In an NMR experimental implementation, we generate multipartite entangled states starting from initial separable pseudo-pure states by simulating nearest-neighbor XY interactions in a 3-spin linear chain of nuclear spin qubits. For simulating XY interactions, we follow algebraic method of Zhang et al. Phys. Rev. A 72 (2005) 012331]. Bell state between end qubits has been generated by using only the unitary evolution of the XY Hamiltonian. For generating W-state and GHZ-state a single qubit rotation is applied on second and all the three qubits, respectively after the unitary evolution of the XY Hamiltonian.