DNA targeting polyaza macrobicyclic dizinc(II) complexes promoting high in vitro caspase dependent anti-proliferative activity against human carcinoma cancer cells

A series of macrobicyclic dizinc(II) complexes Zn2L1-2B](ClO4)(4) (1-6) have been synthesized and characterized (L1-2 are polyaza macrobicyclic binucleating ligands, and B is the N,N-donor heterocyclic base (viz. 2,2'-bipyridine (bipy) and 1,10-phenanthroline (phen)). The DNA and protein binding, DNA hydrolysis and anticancer activity of these complexes were investigated. The interactions of complexes 1-6 with calf thymus DNA were studied by spectroscopic techniques, including absorption, fluorescence and CD spectroscopy. The DNA binding constant values of the complexes were found to range from 2.80 x 10(5) to 5.25 x 10(5) M-1, and the binding affinities are in the following order: 3 > 6 > 2 > 5 > 1 > 4. All the dizinc(II) complexes 1-6 are found to effectively promote the hydrolytic cleavage of plasmid pBR322 DNA under anaerobic and aerobic conditions. Kinetic data for DNA hydrolysis promoted by 3 and 6 under physiological conditions give observed rate constants (k(obs)) of 5.56 +/- 0.1 and 5.12 +/- 0.2 h(-1), respectively, showing a 10(7)-fold rate acceleration over the uncatalyzed reaction of dsDNA. Remarkably, the macrobicyclic dizinc(II) complexes 1-6 bind and cleave bovine serum albumin (BSA), and effectively promote the caspase-3 and caspase-9 dependent deaths of HeLa and BeWo cancer cells. The cytotoxicity of the complexes was further confirmed by lactate dehydrogenase enzyme levels in cancer cell lysate and content media.

Hot-pressed TiB2-10 wt.% TiSi2 ceramic with extremely good thermal transport properties at elevated temperatures (up to 1273 K)

This contribution reports and analyses the high thermal transport property of hot-pressed TiB2-10 wt.% TiSi2 ceramics. Depending on the test temperature, the thermal conductivity values of the TiB2 composite (which range from 89 to 122W m(-1) K-1) are determined to be 18-25% higher than that of monolithic TiB2. The thermal transport properties are analyzed in terms of electronic and phonon contributions. The electronic contribution is the major component of the thermal conductivity of TiB2 and comparable contributions from both electronic and phonon components are observed for the TiB2-TiSi2 composite. (C) 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

System Ho-Rh-O: Phase Equilibria, Chemical Potentials and Gibbs Energy of Formation of HoRhO3

The thermodynamic properties of the HoRhO3 were determined in the temperature range from 900 to 1300 K by using a solid-state electrochemical cell incorporating calcia-stabilized zirconia as the electrolyte. The standard Gibbs free energy of formation of orthorhombic perovskite HoRhO3, from Ho2O3 with C-rare earth structure and Rh2O3 with orthorhombic structure, can be expressed by the equation; Delta G(f)degrees((ox)) (+/- 78)/(J/mol) = -50535 + 3.85(T/K) Using the thermodynamic data of HoRhO3 and auxiliary data for binary oxides from the literature, the phase relations in the Ho-Rh-O system were computed at 1273 K. Thermodynamic data for intermetallic phases in the binary Ho-Rh were estimated from experimental enthalpy of formation for three compositions from the literature and Miedema's model, consistent with the phase diagram. The oxygen potential-composition diagram and three-dimensional chemical potential diagram at 1273 K, and temperature-composition diagrams at constant oxygen partial pressures were computed for the system Ho-Rh-O. The decomposition temperature of HoRhO3 is 1717(+/- 2) K in pure O-2 and 1610(+/- 2) K in air at a total pressure p(o) = 0.1 MPa.

Raman scattering, microstructural and dielectric studies on Ba1-xCaxBi4Ti4O15 ceramics

Polycrystalline powders of Ba1-xCaxBi4Ti4O15 (where x = 0, 0.25, 0.50, 0.75 and 1) were prepared via the conventional solid-state reaction route. X-ray diffraction (XRD) and Raman scattering techniques have been employed to probe into the structural changes on changing x. XRD analyses confirmed the formation of monophasic bismuth layered structure of all the above compositions with an increase in orthorhombic distortion with increase in x. Raman spectra revealed a redshift in A(1g) peak and an increase in the B-2g/B-3g splitting with increasing Ca content. The average grain size was found to increase with increasing x. The temperature of the maximum dielectric constant (T-m) increased linearly with increasing Ca-content whereas the diffuseness of the phase transition was found to decrease with the end member CaBi4Ti4O15 showing a frequency independent sharp phase transition around 1048 K. Ca doping resulted in a decrease in the remnant polarization and an increase in the coercive field. Ba0.75Ca0.25Bi4Ti4O15 ceramics showed an enhanced piezoelectric coefficient d(33) of 15 pC N-1 at room temperature. Low values of dielectric losses and tunability of temperature coefficient of dielectric constant (tau(epsilon)) in the present solid-solution suggest that these compounds can be of potential use in microwave dielectrics at high temperatures. (C) 2012 Elsevier B.V. All rights reserved.

Stochastically driven instability in rotating shear flows

The origin of hydrodynamic turbulence in rotating shear flows is investigated, with particular emphasis on the flows whose angular velocity decreases but whose specific angular momentum increases with the increasing radial coordinate. Such flows are Rayleigh stable, but must be turbulent in order to explain the observed data. Such a mismatch between the linear theory and the observations/experiments is more severe when any hydromagnetic/magnetohydrodynamic instability and then the corresponding turbulence therein is ruled out. This work explores the effect of stochastic noise on such hydrodynamic flows. We essentially concentrate on a small section of such a flow, which is nothing but a plane shear flow supplemented by the Coriolis effect. This also mimics a small section of an astrophysical accretion disc. It is found that such stochastically driven flows exhibit large temporal and spatial correlations of perturbation velocities and hence large energy dissipations of perturbation, which presumably generate the instability. A range of angular velocity (Omega) profiles of the background flow, starting from that of a constant specific angular momentum (lambda = Omega r(2); r being the radial coordinate) to a constant circular velocity (v(phi) = Omega r), is explored. However, all the background angular velocities exhibit identical growth and roughness exponents of their perturbations, revealing a unique universality class for the stochastically forced hydrodynamics of rotating shear flows. This work, to the best of our knowledge, is the first attempt to understand the origin of instability and turbulence in three-dimensional Rayleigh stable rotating shear flows by introducing additive noise to the underlying linearized governing equations. This has important implications to resolve the turbulence problem in astrophysical hydrodynamic flows such as accretion discs.

Thermodynamics of TmRhO3, Phase Equilibria, and Chemical Potentials in the System Tm-Rh-O

Phase equilibria in the system Tm-Rh-O at 1200 K is established by isothermal equilibration of selected compositions and phase identification after quenching to room temperature. Six intermetallic phases (Tm3Rh, Tm7Rh3, Tm5Rh3, Tm3Rh2, TmRh, TmRh2 +/-delta) and a ternary oxide TmRhO3 are identified. Based on experimentally determined phase relations, a solid-state electrochemical cell is devised to measure the standard free energy of formation of orthorhombic perovskite TmRhO3 from cubic Tm2O3 and beta-Rh2O3 in the temperature range from (900 to 1300) K. The results can be summarized as: Delta G(f,ox)(o) +/- 104/J.mol(-1) = -46474 + 3.925(T/K). Invoking the Neumann-Kopp rule, the standard enthalpy of formation of TmRhO3 from its constituent elements at 298.15 K is estimated as -1193.89 (+/- 2.86) kJ.mol(-1). The standard entropy of TmRhO3 at 298.15 K is evaluated as 103.8 (+/- 1.6) J.mol(-1).K-1. The oxygen potential-composition diagram and three-dimensional chemical potential diagram at 1200 K and temperature-composition diagrams at constant partial pressures of oxygen are computed from thermodynamic data. The compound TmRhO3 decomposes at 1688 (+/- 2) K in pure oxygen and at 1583 (+/- 2) K in air at standard pressure.

Cobalt(II), Nickel(II) and Copper(II) complexes of a tetradentate Schiff base as photosensitizers: Quantum yield of O-1(2) generation and its promising role in anti-tumor activity

In the present investigation, a Schiff base N'(1),N'(3)-bis(E)-(5-bromo-2-hydroxyphenyl)methylidene]benzene-1,3-d icarbohydrazide and its metal complexes have been synthesized and characterized. The DNA-binding studies were performed using absorption spectroscopy, emission spectra, viscosity measurements and thermal denatuaration studies. The experimental evidence indicated that, the Co(II), Ni(II) and Cu(II) complexes interact with calf thymus DNA through intercalation with an intrinsic binding constant K-b of 2.6 x 10(4) M-1, 5.7 x 10(4) M-1 and 4.5 x 10(4) M-1, respectively and they exhibited potent photo-damage abilities on pUC19 DNA, through singlet oxygen generation with quantum yields of 0.32, 0.27 and 0.30 respectively. The cytotoxic activity of the complexes resulted that they act as a potent photosensitizers for photochemical reactions. (C) 2012 Elsevier B.V. All rights reserved.

The irradiation of pure CH3OH and 1:1 mixture of NH3:CH3OH ices at 30 K using low energy electrons

The results of an experimental investigation of 1 keV electron irradiation of ices (deposited at 30 K) of (i) pure methanol and (ii) of a 1:1 mixture of NH3:CH3OH are reported. Molecular products formed within the ice were detected and monitored using FTIR spectroscopy. The products observed were methyl formate (H3COHCO), methane (CH4), hydroxymethyl (CH2OH), formamide (HCONH2), formic acid (HCOOH), formaldehyde (H2CO), formyl radical (HCO), cyanate ion (OCN-), isocyanic acid (HNCO), carbon monoxide (CO) and carbon dioxide (CO2). The consequences of these results for prebiotic chemistry in the interstellar medium and star forming regions are discussed. Crown Copyright (C) 2012 Published by Elsevier B. V. All rights reserved.

Minimum power consumption for drag reduction on a circular cylinder by tangential surface motion

We investigate the effect of a prescribed tangential velocity on the drag force on a circular cylinder in a spanwise uniform cross flow. Using a combination of theoretical and numerical techniques we make an attempt at determining the optimal tangential velocity profiles which will reduce the drag force acting on the cylindrical body while minimizing the net power consumption characterized through a non-dimensional power loss coefficient (C-PL). A striking conclusion of our analysis is that the tangential velocity associated with the potential flow, which completely suppresses the drag force, is not optimal for both small and large, but finite Reynolds number. When inertial effects are negligible (R e << 1), theoretical analysis based on two-dimensional Oseen equations gives us the optimal tangential velocity profile which leads to energetically efficient drag reduction. Furthermore, in the limit of zero Reynolds number (Re -> 0), minimum power loss is achieved for a tangential velocity profile corresponding to a shear-free perfect slip boundary. At finite Re, results from numerical simulations indicate that perfect slip is not optimum and a further reduction in drag can be achieved for reduced power consumption. A gradual increase in the strength of a tangential velocity which involves only the first reflectionally symmetric mode leads to a monotonic reduction in drag and eventual thrust production. Simulations reveal the existence of an optimal strength for which the power consumption attains a minima. At a Reynolds number of 100, minimum value of the power loss coefficient (C-PL = 0.37) is obtained when the maximum in tangential surface velocity is about one and a half times the free stream uniform velocity corresponding to a percentage drag reduction of approximately 77 %; C-PL = 0.42 and 0.50 for perfect slip and potential flow cases, respectively. Our results suggest that potential flow tangential velocity enables energetically efficient propulsion at all Reynolds numbers but optimal drag reduction only for Re -> infinity. The two-dimensional strategy of reducing drag while minimizing net power consumption is shown to be effective in three dimensions via numerical simulation of flow past an infinite circular cylinder at a Reynolds number of 300. Finally a strategy of reducing drag, suitable for practical implementation and amenable to experimental testing, through piecewise constant tangential velocities distributed along the cylinder periphery is proposed and analysed.

Evaluation of Fracture Parameters by Double-G, Double-K Models and Crack Extension Resistance for High Strength and Ultra High Strength Concrete Beams

This paper presents the advanced analytical methodologies such as Double- G and Double - K models for fracture analysis of concrete specimens made up of high strength concrete (HSC, HSC1) and ultra high strength concrete. Brief details about characterization and experimentation of HSC, HSC1 and UHSC have been provided. Double-G model is based on energy concept and couples the Griffith's brittle fracture theory with the bridging softening property of concrete. The double-K fracture model is based on stress intensity factor approach. Various fracture parameters such as cohesive fracture toughness (4), unstable fracture toughness (K-Ic(c)), unstable fracture toughness (K-Ic(un)) and initiation fracture toughness (K-Ic(ini)) have been evaluated based on linear elastic fracture mechanics and nonlinear fracture mechanics principles. Double-G and double-K method uses the secant compliance at the peak point of measured P-CMOD curves for determining the effective crack length. Bi-linear tension softening model has been employed to account for cohesive stresses ahead of the crack tip. From the studies, it is observed that the fracture parameters obtained by using double - G and double - K models are in good agreement with each other. Crack extension resistance has been estimated by using the fracture parameters obtained through double - K model. It is observed that the values of the crack extension resistance at the critical unstable point are almost equal to the values of the unstable fracture toughness K-Ic(un) of the materials. The computed fracture parameters will be useful for crack growth study, remaining life and residual strength evaluation of concrete structural components.

Electrochemical determination of thermodynamic properties of DyRhO3 and phase relations in the system Dy-Rh-O

Thermodynamic properties of Dysprosium rhodite (DyRhO3) are measured in the temperature range from 900 to 1,300 K using a solid-state electrochemical cell incorporating yttria-stabilized zirconia as the electrolyte. The standard Gibbs free energy of formation of DyRhO3 with O-type perovskite structure from its components binary oxides, Dysprosia with C-rare earth structure and beta-Rh2O3 with orthorhombic structure, can be represented by the equation: Delta G(f(OX))(O) (+/- 182)/J mol(-1) = -52710+3.821(T/K). By using the thermodynamic data for DyRhO3 from experiment and auxiliary data for other phases from the literature, the phase relations in the system Dy-Rh-O are computed. Thermodynamic data for intermetallic phases in the binary system Dy-Rh, required for constructing the chemical potential diagrams, are evaluated using calorimetric data available in the literature for three intermetallics and Miedema's model, consistent with the phase diagram. The results are presented in the form of Gibbs triangle, oxygen potential-composition diagram, and three-dimensional chemical potential diagram at 1,273 K. Temperature-composition diagrams at constant oxygen partial pressures are also developed. The decomposition temperature of DyRhO3 is 1,732 (+/- 2.5) K in pure oxygen and 1,624 (+/- 2.5) K and in air at standard pressure.

Capacity region of K-user discrete memoryless interference channels with a mixed strong-very strong interference

The capacity region of the 3-user Gaussian Interference Channel (GIC) with mixed strong-very strong interference was established in [1]. The mixed strong-very strong interference conditions considered in [1] correspond to the case where, at each receiver, one of the interfering signals is strong and the other is very strong. In this paper, we derive the capacity region of K-user (K ≥ 3) Discrete Memoryless Interference Channels (DMICs) with a mixed strong-very strong interference. This corresponds to the case where, at each receiver one of the interfering signals is strong and the other (K - 2) interfering signals are very strong. This includes, as a special case, the 3-user DMIC with mixed strong-very strong interference. The proof is specialized to the 3-user GIC case and hence an alternative derivation for the capacity region of the 3-user GIC with mixed strong-very strong interference is provided.

On the generalized degrees of freedom of the K-user symmetric MIMO Gaussian interference channel

This work derives inner and outer bounds on the generalized degrees of freedom (GDOF) of the K-user symmetric MIMO Gaussian interference channel. For the inner bound, an achievable GDOF is derived by employing a combination of treating interference as noise, zero-forcing at the receivers, interference alignment (IA), and extending the Han-Kobayashi (HK) scheme to K users, depending on the number of antennas and the INR/SNR level. An outer bound on the GDOF is derived, using a combination of the notion of cooperation and providing side information to the receivers. Several interesting conclusions are drawn from the bounds. For example, in terms of the achievable GDOF in the weak interference regime, when the number of transmit antennas (M) is equal to the number of receive antennas (N), treating interference as noise performs the same as the HK scheme and is GDOF optimal. For K >; N/M+1, a combination of the HK and IA schemes performs the best among the schemes considered. However, for N/M <; K ≤ N/M+1, the HK scheme is found to be GDOF optimal.

k.p based closed form energy band gap and transport electron effective mass model for 100] and 110] relaxed and strained Silicon nanowire

In this paper, we address a physics based closed form model for the energy band gap (E-g) and the transport electron effective mass in relaxed and strained 100] and 110] oriented rectangular Silicon Nanowire (SiNW). Our proposed analytical model along 100] and 110] directions are based on the k.p formalism of the conduction band energy dispersion relation through an appropriate rotation of the Hamiltonian of the electrons in the bulk crystal along 001] direction followed by the inclusion of a 4 x 4 Luttinger Hamiltonian for the description of the valance band structure. Using this, we demonstrate the variation in Eg and the transport electron effective mass as function of the cross-sectional dimensions in a relaxed 100] and 110] oriented SiNW. The behaviour of these two parameters in 100] oriented SiNW has further been studied with the inclusion of a uniaxial strain along the transport direction and a biaxial strain, which is assumed to be decomposed from a hydrostatic deformation along 001] with the former one. In addition, the energy band gap and the effective mass of a strained 110] oriented SiNW has also been formulated. Using this, we compare our analytical model with that of the extracted data using the nearest neighbour empirical tight binding sp(3)d(5)s* method based simulations and has been found to agree well over a wide range of device dimensions and applied strain. (C) 2012 Elsevier Ltd. All rights reserved.

Fatigue Crack Growth Study and Remaining Life Assessment of High Strength and Ultra High Strength Concrete Beams

This paper presents the details of crack growth study and remaining life assessment of concrete specimens made up of high strength concrete (HSC, HSC1) and ultra high strength concrete (UHSC). Flexural fatigue tests have been conducted on HSC, HSC1 and UHSC beams under constant amplitude loading with a stress ratio of 0.2. It is observed from the studies that (i) the failure patterns of HSC1 and UHSC beams indicate their ductility as the member was intact till the crack propagated up to 90% of the beam depth and (ii) the remaining life decreases with increase of notch depth (iii) the failure of the specimen is influenced by the frequency of loading. A ``Net K'' model has been proposed by using non-linear fracture mechanics principles for crack growth analysis and remaining life prediction. SIF (K) has been computed by using the principle of superposition. SIP due to the cohesive forces applied on the effective crack face inside the process zone has been obtained through Green's function approach by applying bi-linear tension softening relationship to consider the cohesive the stresses acting ahead of the crack tip. Remaining life values have been have been predicted and compared with the corresponding experimental values and observed that they are in good agreement with each other.