Chelating and bridging bis(diphenylphosphino)aniline complexes of copper(I)

The ligand bis(diphenylphosphino)aniline (dppan) has been shown to be a versatile ligand sporting different coordination modes and geometries as dictated by copper(I) and the counter ion. The molecular structures of its Cu(I) complexes were characterized by X-ray crystallography. The ligand was found in a chelating mode and monomeric complexes were formed when the ligand to copper ratio was 2: 1 and the anion was non-coordinating. However, with thiocyanate as the counter anion, the ligand was found to adopt two different modes, with one ligand chelating and the other acting as a monodentate ligand. With CuX (X = Cl, Br), dppan formed a tetrameric complex when the ligand and metal were reacted in the ratio of 1:1. But reactions containing ligand and metal in the ratios of 1: 2 or 2: 1, resulted in the formation of a mixture of species in solution. Crystallization however, led to the isolation of the tetrameric complex. Variable temperature P-31{H-1} NMR spectra of the isolated tetramers did not show the presence of chelated structures in solution. Tetra-alkylammonium salts were added to solutions of various complexes of dppan and studied by P-31{H-1} NMR to probe the effect of anions on the stability of complexes in solution. The Cu-dppan complexes were robust and did not interconvert with other structures in solution unlike the bis(diphenylphosphino) isopropylamine complexes. (C) 2011 Elsevier B.V. All rights reserved.

Universal behaviour in erosive burning of solid propellants

This paper considers the extensive data and correlations on the erosive burning of solid propellants. A relatively simple nondimensional relationship between the ratio of the actual to nonerosive burn rate (eta) and a quantity g, which is the product of g(0)-the ratio of free stream mass flux to the mass flux from the surface for nonerosive condition-and Re-0(m), where Re-0 is the Reynolds number based on the nonerosive mass flux of the propellant and port diameter, is shown to correlate most data within the accuracies of the experiments with m = -0.125. This shows the above relationship to account for the effects of pressure, aluminum, even up to a proportion of 17%, burn rate catalysts, and motor size. It is concluded that the suggested correlation between eta and g may be adopted universally for most practical propellants. (C) 1997 by The Combustion Institute.

Structural characterisation of a uracil containing hairpin DNA by NMR and molecular dynamics

Three-dimensional (3D) structure of a hairpin DNA d-CTAGAGGATCCTTTUGGATCCT (22mer; abbreviated as U4-hairpin), which has a uracil nucleotide unit at the fourth position from the 5' end of the tetra-loop has been solved by NMR spectroscopy. The H-1 resonances of this hairpin have been assigned almost completely. NMR restrained molecular dynamics and energy minimisation procedures have been used to describe the 3D structure of the U4 hairpin. This study establishes that the stem of the hairpin adopts a right handed B-DNA conformation while the T-12 and U-15 nucleotide stack upon 3' and 5' ends of the stem, respectively. Further, T-14 stacks upon both T-12 and U-15 while T-13 partially stacks upon T-14. Very weak stacking interaction is observed between T-13 and T-12. All the individual nucleotide bases adopt 'anti' conformation with respect to their sugar moiety. The turning phosphate in the loop is located between T-13 and T-14. The stereochemistry of U-15 mimics the situation where uracil would stack in a B-DNA conformation. This could be the reason as to why the U4-hairpin is found to be the best substrate for its interaction with uracil DNA glycosylase (UDG) compared to the other substrates in which the uracil is at the first, second and third positions of the tetra-loop from its 5' end, as reported previously.

Synthesis and properties of La1-xSrxFeO3

Fine particle strontium substituted lanthanum ferrites La1-xSrxFeO3, where x = 0.0-1.0, have been synthesized by the solution combustion method using corresponding metal nitrates, oxalyl dihydrazide (ODH) or tetra formal tris azine (TFTA). Formation of La1-xSrxFeO3 was confirmed by the XRD and the fine particle nature of the ferrites investigated using SEM, particle size analysis and BET surface area measurements. La1-xSrxFeO3 (up to x = 0-0.4) exhibited low resistivity near the Neel temperatures. La1-xSrxFeO3 with x greater than or equal to 0.8 when used as bifunctional electrodes, showed oxygen evolution and reduction activity comparable with the orthoferrites prepared by the conventional solid state method. (C) 1999 Elsevier Science B.V. All rights reserved.

Chromatographic methods for determination of nimesulide and for stability studies

Simple and rapid HPLC, GC, and TLC procedures have been developed for detection and determination of nimesulide, a non-pharmacopeial drug, in preformulation and dosage form. Use of these techniques has enabled separation of impurities and the precursor in the bulk material and in formulations. Isocratic reversed-phase HPLC was performed on a C-18 column with methanol-water-acetic acid, 67:32:1 (v/v), as mobile phase and UV detection at 230 nm. Calibration curves were linear over the concentration range 100-1000 mug mL(-1) with a good correlation coefficient (0.9993) and a coefficient of variation of 1.5%. Gas chromatography was performed on an OV-17 packed column with temperature programming and flame-ionization detection. The lower limit of determination by HPLC and GC was 4 ppm. Thin-layer chromatography of nimesulide was performed on silica gel G with toluene-ethyl acetate, 8:2, as mobile phase. Stability testing of the drug was performed under different temperature, humidity, and UV-radiation conditions.

Sandwich propellant combustion: Modeling and experimental comparison

This paper reports reacting fluid dynamics calculations for an ammonium percholrate binder sandwich and extracts experimentally observed features including surface profiles and maximum regression rates as a function of pressure and binder thickness. These studies have been carried out by solving the two-dimensional unsteady Navier-Stokes equations with energy and species conservation equations and a kinetic model of three reaction steps (ammonium perchlorate decomposition flame, primary diffusion flame, and final diffusion flame) in the gas phase. The unsteady two-dimensional conduction equation is solved in the condensed phase. The regressing surface is unsteady and two dimensional. Computations have been carried out for a binder thickness range of 25-125 mum and a pressure range of 1.4 to 6.9 MPa. Good comparisons at several levels of detail are used to demonstrate the need for condensed-phase two-dimensional unsteady conduction and three-step gas-phase reactions. The choice of kinetic and thermodynamic parameters is crucial to good comparison with experiments. The choice of activation energy parameters for ammonium percholrate combustion has been made with stability of combustion in addition to experimentally determined values reported in literature. The choice of gas-phase parameters for the diffusion flames are made considering that (a) primary diffusion flame affects the low-pressure behavior and (b) final diffusion flame affects high-pressure behavior. The predictions include the low-pressure deflagration limit of the sandwich apart from others noted above. Finally, this study demonstrates the possibility of making meaningful comparisons with experimental observations on sandwich propellant combustion.

Studies on a new high-intensity low-emission burner

This paper presents computational and experimental results on a new burner configuration with a mild combustion concept with heat release rates up to 10 MW/m(3). The burner configuration is shown to achieve mild combustion by using air at ambient temperature at high recirculation rates (similar to250%-290%) both experimentally and computationally. The principal features of the configuration are: (1) a burner with forward exit for exhaust gases; (2) injection of gaseous fuel and air as multiple, alternate, peripheral highspeed jets at the bottom at ambient temperature, thus creating high enough recirculation rates of the hot combustion products into fresh incoming reactants; and (3) use of a suitable geometric artifice-a frustum of a cone to help recirculation. The computational studies have been used to reveal the details of the flow and to optimize the combustor geometry based on recirculation rates. Measures, involving root mean square temperature fluctuations, distribution of temperature and oxidizer concentration inside the proposed burner, and a classical turbulent diffusion jet flame, are used to distinguish between them quantitatively. The system, operated at heat release rates of 2 to 10 MW/m(3) (compared to 0.02 to 0.32 MW/m(3) in the earlier studies), shows a 10-15 dB reduction in noise in the mild combustion mode compared to a simple open-top burner and exhaust NOx emission below 10 ppm for a 3 kW burner with 10% excess air. The peak temperature is measured around 1750 K, approximately 300 K lower than the peak temperature in a conventional burner.

Synthesis, biological studies of linear and branched arabinofuranoside-containing glycolipids and their interaction with surfactant protein A

Oligoarabinofuranoside-containing glycolipids relevant to mycobacterial cell wall components were synthesized in order to understand the functional roles of such glycolipids. A series of linear tetra-, hexa-, octa-and a branched heptasaccharide oligoarabinofuranosides, with 1 -> 2 and 1 -> 5 a-linkages between the furanoside residues, were synthesized by chemical methods from readily available monomer building blocks. Upon the synthesis of glycolipids, constituted with a double alkyl chain-substituted sn-glycerol core and oligosaccharide fragments, biological studies were performed to identify the effect of synthetic glycolipids on the biofilm formation and sliding motilities of Mycobacterium smegmatis. Synthetic glycolipids and arabinofuranosides displayed an inhibitory effect on the growth profile, but mostly on the biofilm formation and maturation. Similarly, synthetic compounds also influenced the sliding motility of the bacteria. Further, biophysical studies were undertaken, so as to identify the interactions of the glycolipids with a pulmonary surfactant protein, namely surfactant protein A (SP-A), with the aid of the surface plasmon resonance technique. Specificities of each glycolipid interacting with SP-A were thus evaluated. From this study, glycolipids were found to exhibit higher apparent association constants than the corresponding oligosaccharide portion alone, without the double alkyl group-substituted glycerol core.

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.

Relationship Between Physical Structure and Tribology of Single Soot Particles Generated by Burning Ethylene

Ethylene gas is burnt and the soot generated is sampled thermophoretically at different heights along the flame axis starting from a region close to the root of the flame. The morphology and crystallinity of the particle are recorded using high resolution transmission electron microscopes. The hardness of a single particle is measured using a nanoindenter. The frictional resistance and material removal of a particle are measured using an atomic force microscope. The particles present in the mid-flame region are found to have a crystalline shell. The ones at the flame root are found to be highly disordered and the ones at the flame tip and above have randomly distributed pockets of short range order. The physical state of a particle is found to relate, but not very strongly, with the mechanical and tribological properties of the particles.

Experimental and Numerical Studies in a Compact Trapped Vortex Combustor: Stability Assessment and Augmentation

Fundamental studies on a compact trapped vortex combustor indicate that cavity injection strategies play a major role on flame stability. Detailed experiments indicate that blow-out occurs for a certain range of cavity air flow velocities. An unsteady RANS-based reacting flow simulation tool has been utilized to study the basic dynamics of cavity vortex for various flow conditions. The phenomenon of flame blow-out at certain intermediate cavity air velocities is explained on the basis of transition from a cavity-stabilized mode to an opposed flow stagnation mode. A novel strategy is proposed for achieving flame stability at all conditions. This involves using a flow guide vane in the path of the main flow to direct a portion of the main flow into the cavity. This seems to result in a desirable dual vortex structure, i.e., a small clockwise vortex behind the vane and large counterclockwise vortex in the cavity. Experimental results show stable flame at all flow conditions with the flow guide vane, and pressure drop is estimated to be within acceptable limits. Cold flow simulations show self-similar velocity profiles for a range of main inlet velocities, and high reverse velocity ratios (-0.3) are observed. Such a high-velocity ratio in the reverse flow shear layer profile leads to enhanced production of turbulence imperative to compact combustors. Reacting flow simulations show even higher reverse velocity ratios (above -0.7) due to flow acceleration. The flame is observed to be stable, even though minor shear layer oscillations are present in the form of vortex shedding. Self-similarity is also observed in reacting flow temperature profiles at combustor exit over the entire range of the mainstream velocity. This indicates that the present configuration holds a promise of delivering robust performance invariant of the flow operating conditions.

Optical, electrical and dielectric properties of TiO(2)-SiO(2) films prepared by a cost effective sol-gel process

Titanium dioxide (TiO(2)) and silicon dioxide (SiO(2)) thin films and their mixed films were synthesized by the sol-gel spin coating method using titanium tetra isopropoxide (TTIP) and tetra ethyl ortho silicate (TEOS) as the precursor materials for TiO(2) and SiO(2) respectively. The pure and composite films of TiO(2) and SiO(2) were deposited on glass and silicon substrates. The optical properties were studied for different compositions of TiO(2) and SiO(2) sols and the refractive index and optical band gap energies were estimated. MOS capacitors were fabricated using TiO(2) films on p-silicon (1 0 0) substrates. The current-voltage (I-V) and capacitance-voltage (C-V) characteristics were studied and the electrical resistivity and dielectric constant were estimated for the films annealed at 200 degrees C for their possible use in optoelectronic applications. (C) 2011 Elsevier B.V. All rights reserved.

Carbon potential measurements on some actinide carbides

Uranium-Plutonium mixed carbide with a Pu/(U+Pu) ratio of 0.55 is to be used as the fuel in the Fast Breeder Test Reaotor - (PBTRj at Kalpakkam, India. carbur ization of the stainlese steel clad by this fuel is determined by its carbon potential. - i. Because the carbon potential of this fuel composition is not 1 available in the literature, it was meadured by the methanehydrogen gas equilibration technique. The sample was equilibrated with purified hydrogen and the equilibrium methane-tohydrogen ratio in the gas phase was measured with a flame ionization detector. The carbon potential of the ThC-ThCz as well as Mo-Mo2C system,whiah is an important binary in the aotinide-fission product-carbon systems, were also measured by this technique, in the temperature range 973 K to 1173 K. The data for ! the Mo-MozC system are in agreement with values reported in the literature. The results for the ThC-ThC2 system are different from estimated values with large unaertainty limits given in the literature. The data on (U,Pu) mixed carbide indicates possibility of stainlesss steel clad attack under isothermal equilibrium conditions.

Interaction of G-Quadruplexes with Nonintercalating Duplex-DNA Minor Groove Binding Ligands

The enzyme telomerase synthesizes the G-rich DNA strands of the telomere and its activity is often associated with cancer. The telomerase may be therefore responsible for the ability of a cancer cell-to escape apoptosis. The G-rich DNA sequences often adopt tetra-stranded structure, known as the G-quadruplex DNA (G4-DNA). The stabilization of the telomeric DNA into the G4-DNA structures by small molecules has been the focus of many researchers for the design and development of new anticancer agents. The compounds which stabilize the G-quadruplex in the telomere inhibit the telomerase activity. Besides telomeres, the G4-DNA forming sequences are present in the genomic regions of biological significance including the transcriptional regulatory and promoter regions of several oncogenes. Inducing a G-quadruplex structure within the G-rich promoter sequences is a potential way of achieving selective gene regulation. Several G-quadruplex stabilizing ligands are known. Minor groove binding ligands (MGBLs) interact with the double-helical DNA through the minor grooves sequence-specifically and interfere with several DNA associated processes. These MGBLs when suitably modified switch their preference sometimes from the duplex DNA to G4-DNA and stabilize the G4-DNA as well. Herein, we focus on the recent advances in understanding the G-quadruplex structures, particularly made by the human telomeric ends, and review the results of various investigations of the interaction of designed organic ligands with the G-quadruplex DNA while highlighting the importance of MGBL-G-quadruplex interactions.

Validation of a Modified Eddy Dissipation Concept Model for Stationary and Nonstationary Turbulent Diffusion Flames

A transient flame simulation tool based on unsteady Reynolds average Navier Stokes (RANS) is characterized for stationary and nonstationary flame applications with a motivation of performing computationally affordable flame stability studies. Specifically, the KIVA-3V code is utilized with incorporation of a recently proposed modified eddy dissipation concept for simulating turbulence-chemistry interaction along with a model for radiation loss. Detailed comparison of velocities, turbulent kinetic energies, temperature, and species are made with the experimental data of the turbulent, non-premixed DLR_A CH4/H-2/N-2 jet flame. The comparison shows that the model is able to predict flame structure very well. The effect of some of the modeling assumptions is assessed, and strategies to model a stationary diffusion flame are recommended. Unsteady flame simulation capabilities of the numerical model are assessed by simulating an acoustically excited, experimental, oscillatory H-2-air diffusion flame. Comparisons are made with oscillatory velocity field and OH plots, and the numerical code is observed to predict transient flame structure well.