Ternary copper(II) complexes of thiosemicarbazones and heterocyclic bases showing N3OS coordination as models for the type-2 centers of copper monooxygenases

Six ternary copper(II) complexes of general formulation [CuLB] (1-6), where L is dianionic ONS-donor thiosemicarbazones derived from the condensation of salicylaldehyde with thiosemicarbazides and B is NN-donor heterocyclic bases like 2,2'-bipyridine, 1,10-phenanthroline and 2,9-dimethyl-1,10-phenanthroline, are prepared from a reaction of copper(II) acetate hydrate with the heterocyclic base (B) and the thiosemicarbazone (H2L) in MeOH, and structurally characterized by X-ray diffraction technique. Crystal structures of the complexes display a distorted square-pyramidal (4 + 1) coordination geometry having the ONS-donor thiosemicarbazone bonded at the basal plane. The chelating heterocyclic bases exhibit axial-equatorial mode of bonding. The complexes are one-electron paramagnetic and they show axial X-band EPR spectra in DMF-toluene glass at 77 K giving g(parallel to)(A(parallel to)) and g(perpendicular to) values of similar to2.2 (175 x 10(-4) cm(-1)) and similar to2.0 indicating a {d(x2-y2)}(1) ground state. The complexes show a d-d band near 570 nm and a charge transfer band near 400 nm in DMF. The complexes are redox active and exhibit a quasireversible Cu(II)-Cu(I) couple in DMF-0.1 M tetrabutylammonium perchlorate near 0.1 V vs. SCE. They are catalytically active in the oxidation of ascorbic acid in presence of dioxygen. The complexes with a CuN3OS coordination model the ascorbate oxidation property of dopamine beta-hydroxylase and peptidylglycine a-hydroxylating monooxygeanase. (C) 2003 Elsevier Science B.V. All rights reserved.

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.

Effect of strain path change on the evolution of texture and microstructure during rolling of copper and nickel

The effect of strain path change during rolling has been investigated for copper and nickel using X-ray diffraction and electron back scatter diffraction as well as crystal plasticity simulations. Four different strain paths namely: (i) unidirectional rolling; (ii) reverse rolling; (iii) two-step cross rolling and (iv) multi-step cross rolling were employed to decipher the effect of strain path change on the evolution of deformation texture and microstructure. The cross rolled samples showed weaker texture with a prominent Bs {1 1 0}< 1 1 2 > and P(B(ND)) {1 1 0}< 1 1 1 > component in contrast to the unidirectional and reverse rolled samples where strong S {1 2 3}< 6 3 4 > and Cu {1 1 2}< 1 1 1 > components were formed. This was more pronounced for copper samples compared to nickel. The cross rolled samples were characterized by lower anisotropy and Taylor factor as well as less variation in Lankford parameter. Viscoplastic self-consistent simulations indicated that slip activity on higher number of octahedral slip systems can explain the weaker texture as well as reduced anisotropy in the cross rolled samples. (C) 2011 Elsevier B.V. All rights reserved.

Total synthesis of panaxytriol and panaxydiol

The enantioselective total synthesis of the diyne containing natural products panaxytriol and (3S,10R)-panaxydiol from L-tartaric acid is reported. Key steps in the synthesis include the elaboration of a gamma-hydroxy amide derived from tartaric acid to the required alkyne and the formation of the desired diyne unit by a Cadiot-Chodkiewicz coupling. (C) 2011 Elsevier Ltd. All rights reserved.

Efficient synthesis of carbonyl compounds: oxidation of azides and alcohols catalyzed by vanadium pentoxide in water using tert-butylhydroperoxide

Catalytic amount of vanadium reagent with tert-butylhydroperoxide as the oxidant was found to be an excellent oxidizing agent in aqueous medium. Vanadium pentoxide with aq tert-butylhydroperoxide readily oxidizes primary benzylic azides to the corresponding acids and secondary benzylic azides to the corresponding ketones in excellent yields. Further, vanadium pentoxide and aq tert-butylhydroperoxide combination turned out to be an effective catalyst for the oxidation of alcohols. Using vanadium pentoxide and aq tert-butylhydroperoxide primary alcohols were oxidized to the corresponding acids, whereas secondary alcohols underwent a smooth transformation to furnish corresponding ketones in excellent yields. All the oxidations are performed in water. (C) 2011 Elsevier Ltd. All rights reserved.

Electrochemical performance of mixed crystallographic phase nanotubes and nanosheets of titania and titania-carbon/silver composites for lithium-ion batteries

The role of homogeneity in ex situ grown conductive coatings and dimensionality in the lithium storage properties of TiO(2) is discussed here. TiO(2) nanotube and nanosheet comprising of mixed crystallographic phases of anatase and TiO(2) (B) have been synthesized by an optimized hydrothermal method. Surface modifications of TiO(2) nanotube are realized via coating the nanotube with Ag nanoparticles and amorphous carbon. The first discharge cycle capacity (at current rate = 10 mA g(-1)) for TiO(2) nanotube and nanosheet were 355 mAh g(-1) and 225 mAhg(-1), respectively. The conductive surface coating stabilized the titania crystallographic structure during lithium insertion-deinsertion processes via reduction in the accessibility of lithium ions to the trapping sites. The irreversible capacity is beneficially minimized from 110 mAh g(-1) for TiO(2) nanotubes to 96 mAh g(-1) and 57 mAhg(-1) respectively for Ag and carbon modified TiO(2) nanotubes. The homogeneously coated amorphous carbon over TiO(2) renders better lithium battery performance than randomly distributed Ag nanoparticles coated TiO(2) due to efficient hopping of electrons. (C) 2011 Elsevier B.V. All rights reserved.

Wear behavior of plasma electrolytic oxidation (PEO) and hybrid coatings of PEO and laser on MRI 230D magnesium alloy

Wear resistant coatings were produced on a permanent mould cast MRI 230D Mg alloy by (a) PEO in silicate based electrolyte, (b) PEO in phosphate based electrolyte, (c) hybrid coatings of silicate PEO followed by laser surface alloying (LSA) with Al and Al(2)O(3), and (d) hybrid coatings of phosphate PEO followed by LSA with Al and Al(2)O(3). Microstructural characterization of the coatings was carried out by scanning electron microscopy (SEM) and X(ray diffraction. The tribological behavior of the coatings was investigated under dry sliding condition using linearly reciprocating ball-on-flat wear test. Both the PEO coatings exhibited a friction coefficient of about 0.8 and hybrid coatings exhibited a value of about 0.5 against the AISI 52100 steel ball as the friction partner, which were slightly reduced with the increase in applied load. The PEO coatings sustained the test without failure at 2 N load but failed at 5 N load due to micro-fracture caused by high contact stresses. The hybrid coatings did not get completely worn off at 2 N load but were completely removed exposing the substrate at 5 N load. The PEO coatings exhibited better wear resistance than the hybrid coatings and silicate PEO coatings exhibited better wear resistance than the phosphate PEO coatings. Both the PEO coatings melted/decomposed on laser irradiation and all the hybrid coatings exhibited similar microstructure and wear behavior irrespective of the nature of the primary PEO coating or laser energies. SEM examination of worn surfaces indicated abrasive wear combined with adhesive wear for all the specimens. The surface of the ball exhibited a discontinuous transfer layer after the wear test. (C) 2011 Elsevier B.V. All rights reserved.

Highly efficient dialkylphosphate-mediated syntheses of hydantoins and a bicyclohydantoin under solvent-free conditions

Diversely substituted hydantoins have been synthesized by new strategy from cyanamide based precursor, that is, methyl N-cyano-N-alkyl/arylaminoacetate. Dialkylphosphates were employed as the mild reagent to hydrolyze and cyclize the substrate in one step to give quantitative yields of the desired products. Syntheses of multivalent hydantoins viz bis-hydantoin, bicyclohydantoin have potentially widened the scope and applicability of the present method. Solvent-free conditions and very easy work-up procedure make the reaction convenient and eco-friendly. Single crystal structures of some of the representative compounds are also reported. (C) 2011 Elsevier Ltd. All rights reserved.

Dispersion and vaporization of biofuels and conventional fuels in a crossflow pre-mixer

In lean premixed pre-vaporized (LPP) combustion, controlled atomization, dispersion and vaporization of different types of liquid fuel in the premixer are the key factors required to stabilize the combustion process and improve the efficiency. The dispersion and vaporization process for biofuels and conventional fuels sprayed into a crossflow pre-mixer have been simulated and analyzed with respect to vaporization rate, degree of mixedness and homogeneity. Two major biofuels under investigation are Ethanol and Rapeseed Methyl Esters (RME), while conventional fuels are gasoline and jet-A. First, the numerical code is validated by comparing with the experimental data of single n-heptane and decane droplet evaporating under both moderate and high temperature convective air now. Next, the spray simulations were conducted with monodispersed droplets with an initial diameter of 80 mu m injected into a turbulent crossflow of air with a typical velocity of 10 m/s and temperature of around 800K. Vaporization time scales of different fuels are found to be very different. The droplet diameter reduction and surface temperature rise were found to be strongly dependent on the fuel properties. Gasoline droplet exhibited a much faster vaporization due a combination of higher vapor pressure and smaller latent heat of vaporization compared to other fuels. Mono-dispersed spray was adopted with the expectation of achieving more homogeneous fuel droplet size than poly-dispersed spray. However, the diameter histogram in the zone near the pre-mixer exit shows a large range of droplet diameter distributions for all the fuels. In order to improve the vaporization performance, fuels were pre-heated before injection. Results show that the Sauter mean diameter of ethanol improved from 52.8% of the initial injection size to 48.2%, while jet-A improved from 48.4% to 18.6% and RME improved from 63.5% to 31.3%. The diameter histogram showed improved vaporization performance of jet-A. (C) 2011 Elsevier Ltd. All rights reserved.

In-situ measurements of concentration and temperature during transient solidification of aqueous solution of ammonium chloride using laser interferometry

The variation in temperature and concentration plays a crucial role in predicting the final microstructure during solidification of a binary alloy. Most of the experimental techniques used to measure concentration and temperature are intrusive in nature and affect the flow field. In this paper, the main focus is laid on in-situ, non-intrusive, transient measurement of concentration and temperature during the solidification of a binary mixture of aqueous ammonium chloride solution (a metal-analog system) in a top cooled cavity using laser based Mach-Zehnder Interferometric technique. It was found from the interferogram, that the angular deviation of fringe pattern and the total number of fringes exhibit significant sensitivity to refractive index and hence are functions of the local temperature and concentration of the NH4Cl solution inside the cavity. Using the fringe characteristics, calibration curves were established for the range of temperature and concentration levels expected during the solidification process. In the actual solidification experiment, two hypoeutectic solutions (5% and 15% NH4Cl) were chosen. The calibration curves were used to determine the temperature and concentration of the solution inside the cavity during solidification of 5% and 15% NH4Cl solution at different instants of time. The measurement was carried out at a fixed point in the cavity, and the concentration variation with time was recorded as the solid-liquid interface approached the measurement point. The measurement exhibited distinct zones of concentration distribution caused by solute rejection and Rayleigh Benard convection. Further studies involving flow visualization with laser scattering confirmed the Rayleigh Benard convection. Computational modeling was also performed, which corroborated the experimental findings. (C) 2011 Elsevier Ltd. All rights reserved.

The substrate dependent competitive formation of cyclobutanones and cyclopentanones in an intramolecular rhodium carbenoid CH insertion reaction: enantiospecific total synthesis of silphiperfol-6-ene

The enantiospecific total synthesis of silphiperfol-6-ene has been accomplished starting from the readily available monoterpene (R)-limonene, employing a rhodium carbenoid insertion into the CH bond of a tertiary methyl group. A substrate dependent competitive insertion of the rhodium carbenoid in the gamma- and beta-CH bonds to form cyclopentanone and cyclobutanones, respectively, has been described. (C) 2012 Elsevier Ltd. All rights reserved.

Raman spectroscopic characterization of different regioisomers of monoacyl and diacyl chlorogenic acid

We have investigated the Raman spectra of different regioisomeric forms of monoacyl and diacyl chlorogenic acids. Raman spectra of 3-caffeoylquinic acid, 4-caffeoylquinic acid, 5-caffeoylquinic, 3,4-di-O-caffeoylquinic acid, 3,5-di-O-caffeoylquinic acid, 4,5-di-O-caffeoylquinic acid, and a synthetic derivative of 3-feruloylqunic acid were recorded using visible Raman spectroscopic technique and vibrational bands are assigned. Additionally, a theoretical study of 5-caffeoylquinic acid was performed using Gaussian 03. (C) 2012 Elsevier B.V. All rights reserved.

Functionally graded hydroxyapatite-alumina-zirconia biocomposite: Synergy of toughness and biocompatibility

Functionally Gradient Materials (FGM) are considered as a novel concept to implement graded functionality that otherwise cannot be achieved by conventional homogeneous materials. For biomedical applications, an ideal combination of bioactivity on the material surface as well as good physical property (strength/toughness/hardness) of the bulk is required in a designed FGM structure. In this perspective, the present work aims at providing a smooth gradation of functionality (enhanced toughening of the bulk, and retained biocompatibility of the surface) in a spark plasma processed hydroxyapatite-alumina-zirconia (HAp-Al2O3-YSZ) FGM bio-composite. In the current work HAp (fracture toughness similar to 1.5 MPa.m(1/2)) and YSZ (fracture toughness similar to 62 MPa.m(1/2)) are coupled with a transition layer of Al2O3 allowing minimum gradient of mechanical properties (especially the fracture toughness similar to 3.5 MPa.m(1/2)).The in vitro cyto-compatibilty of HAp-Al2O3-YSZ FGM was evaluated using L929 fibroblast cells and Saos-2 Osteoblast cells for their adhesion and growth. From analysis of the cell viability data, it is evident that FGM supports good cell proliferation after 2, 3, 4 days culture. The measured variation in hardness, fracture toughness and cellular adhesion across the cross section confirmed the smooth transition achieved for the FGM (HAp-Al2O3-YSZ) nanocomposite, i.e. enhanced bulk toughness combined with unrestricted surface bioactivity. Therefore, such designed biomaterials can serve as potential bone implants. (C) 2012 Elsevier B.V. All rights reserved.

Anaerobic retting of banana and arecanut wastes in a plug flow digester for recovery of fiber, biogas and compost

Leaves and leaf sheath of banana and areca husk (Areca catechu) constitute an important component of urban solid waste (USW) in India which are difficult to degrade under normal windrow composting conditions. A successful method of anaerobic digestion built around the fermentation properties of these feedstock has been evolved which uses no moving parts, pretreatment or energy input while enabling recovery of four products: fiber, biogas, compost and pest repellent. An SRT of 27 d and 35 d was found to be optimum for fiber recovery for banana leaf and areca husk, respectively. Banana leaf showed a degradation pattern different from other leaves with slow pectin-1 degradation (80%) and 40% lignin removal in 27 d SRT. Areca husk however, showed a degradation pattern similar to other plant biomass. Mass recovery levels for banana leaf were fiber-20%, biogas-70% (400 ml/g TS) and compost-10%. For areca husk recovery was fiber-50%, biogas-45% (250 ml/g TS) and compost-5%. (C) 2012 Elsevier Inc. All rights reserved.

Development of microstructure and texture in Copper during warm accumulative roll bonding

The evolution of microstructure and texture gradient in warm Accumulative Roll Bonded Cu-Cu multilayer has been studied. Grain size distribution is multimodal and exhibits variation from middle to surface layer. Evolution of texture is largely influenced by shear, in addition to rolling deformation. This leads to the formation of a texture comprising of high fraction of Brass and rolling direction-rotated cube components. Partial recrystallization was observed. Deformed and recrystallized grains were separated using a partition scheme based on grain orientation spread and textures were analyzed for both the partition. Retention of deformation texture components in recrystallized grains suggests the mechanism of recrystallization as continuous recrystallization. Shear deformation plays an important role in grain refinement through continuous recrystallization. (C) 2012 Elsevier Inc. All rights reserved.