Phase behavior of mixtures of polyoxyethylene(10) stearyl ether (Brij-76), 1-butanol, isooctane, and mixed polar solvents I. Water and formamide (or N,N-dimethyl formamide)

The isothermal phase diagram of the quaternary system polyoxyethylene(10) stearyl ether (Brij-76)/1-butanol/isooctane/water has been constructed at 30 degrees C with equal amounts of oil and water. A regular fishtail diagram was obtained, confirming the establishment of hydrophile-lipophile balance (HLB) in the system. Mixing of formamide (FA) [or N,N-dimethyl formamide (DMF)] with water as a cosolvent altered the HLB and decreased the solubilization capacity of the quaternary system. No three-phase body appeared at high FA or DMF content. Similar observations were noted for temperature-induced phase diagrams. The effect of DMF was more pronounced than that of FA in reducing the maximum solubilization capacity. The results have been summarized on the basis of HLB and mutual solubility of the components.     

Stability of dual solutions in stagnation-point flow and heat transfer over a porous shrinking sheet with thermal radiation

An analysis is carried out to study the steady two-dimensional stagnation-point flow and heat transfer of an incompressible viscous fluid over a porous shrinking sheet in the presence of thermal radiation. A set of similarity transformations reduce the boundary layer equations to a set of non-linear ordinary differential equations which are solved numerically using fourth order Runge-Kutta method with shooting technique. The analysis of the result obtained shows that as the porosity parameter β increases, the range of region of existence of similarity solution increases. It is also observed that multiple solutions exist for a certain range of the ratio of the shrinking velocity to the free stream velocity (i.e., α) which again depends on β. We then discuss the stability of the unsteady solutions about each steady solution, showing that one steady state solution corresponds to a stable solution whereas the other corresponds to an unstable solution. The stable solution corresponds to the physically relevant solution. Further we obtain numerical results for each solution, which enable us to discuss the features of the respective solutions.     

Fixation of carbon dioxide by macrocyclic lanthanide(III) complexes under neutral conditions producing self-assembled trimeric carbonato-bridged compounds with μ3-η2:η2:η2 bonding

A series of mononuclear lanthanide(III) complexes [Ln(LH(2))(H(2)O)(3)Cl](ClO(4))(2) (Ln = La, Nd, Sm, Eu, Gd, Tb, Lu) of the tetraiminodiphenolate macrocyclic ligand (LH(2)) in 95 : 5 (v/v) methanol-water solution fix atmospheric carbon dioxide to produce the carbonato-bridged trinuclear complexes [{Ln(LH(2))(H(2)O)Cl}(3)(μ(3)-CO(3))](ClO(4))(4)·nH(2)O. Under similar conditions, the mononuclear Y(III) complex forms the dimeric compound [{Y(LH(2))(H(2)O)Cl}(μ(2)-CO(3)){Y(LH(2))(H(2)O)(2)}](ClO(4))(3)·4H(2)O. These complexes have been characterized by their IR and NMR ((1)H, (13)C) spectra. The X-ray crystal structures have been determined for the trinuclear carbonato-bridged compounds of Nd(III), Gd(III) and Tb(III) and the dinuclear compound of Y(III). In all cases, each of the metal centers are 8-coordinate involving two imine nitrogens and two phenolate oxygens of the macrocyclic ligand (LH(2)) whose two other imines are protonated and intramolecularly hydrogen-bonded with the phenolate oxygens. The oxygen atoms of the carbonate anion in the trinuclear complexes are bonded to the metal ions in tris-bidentate μ(3)-η(2):η(2):η(2) fashion, while they are in bis-bidentate μ(2)-η(2):η(2) mode in the Y(III) complex. The magnetic properties of the Gd(III) complex have been studied over the temperature range 2 to 300 K and the magnetic susceptibility data indicate a very weak antiferromagnetic exchange interaction (J = -0.042 cm(-1)) between the Gd(III) centers (S = 7/2) in the metal triangle through the carbonate bridge. The luminescence spectral behaviors of the complexes of Sm(III), Eu(III), and Tb(III) have been studied. The ligand LH(2) acts as a sensitizer for the metal ions in an acetonitrile-toluene glassy matrix (at 77 K) and luminescence intensities of the complexes decrease in the order Eu(3+) > Sm(3+) > Tb(3+).     

A complete set of self‐consistent charge density‐functional tight‐binding parametrization of zinc chalcogenides (ZnX; X=O,S, Se,and Te)

We have developed a complete set of self‐consistent charge density‐functional tight‐binding parameters for Zn? X (X = Zn, O, S, Se, Te, Cd, H, C, and N). The transferability of the derived parameters has been tested against Pseudo Potential‐Perdew, Burke and Ernzerhof (PP‐PBE) calculations and experimental values (whenever available) for corresponding bulk systems (e.g., hexagonal close packing, zinc‐blende, and wurtzite(wz)), various kinds of nanostructures (such as nanowires, surfaces, and nanoclusters), and also some small molecular systems. Our results show that the derived parameters reproduce the structural and energetic properties of the above‐mentioned systems very well. With the derived parameter set, one can study zinc‐chalcogenide nanostructures of relatively large size which was otherwise prohibited by other methods. The Zn‐Cd parametrization developed in this article will help in studying large semiconductor hetero‐nanostructures of Zn and Cd chalcogenides such as ZnX/CdX core/shell nanoparticles, nanotubes, nanowires, and nanoalloys. © 2012 Wiley Periodicals, Inc.     

Magnetohydrodynamic stagnation-point flow of a power-law fluid towards a stretching surface

Steady two-dimensional stagnation-point flow of an electrically conducting power-law fluid over a stretching surface is investigated when the surface is stretched in its own plane with a velocity proportional to the distance from the stagnation-point. We have discussed the uniqueness of the solution except when the ratio of free stream velocity and stretching velocity is equal to 1. The effect of magnetic field on the flow characteristic is explored numerically and it is concluded that the velocity at a point decreases/increases with increase in the magnetic field when the free stream velocity is less/greater than the stretching velocity. It is further observed that for a given value of magnetic parameter M, the dimensionless shear stress coefficient |F^″(0)| increases with increase in power-law index n when the value of the ratio of free stream velocity and stretching velocity is close to 1 but not equal to 1. But when the value of this ratio further differs from 1, the variation of |F^″(0)| with n is non-monotonic.     

Cost-effective bio-derived mesoporous carbon nanoparticles-supported palladium catalyst for nitroarene reduction and Suzuki–Miyaura coupling by microwave approach

A new heterogeneous catalyst was synthesized by immobilizing Pd on areca nut kernel-derived carbon nanospheres (CNSs). The CNSs, without any further activation processes, accommodated 3% of Pd on their surface. The new Pd/CNS material was used for the reduction of nitroarenes and Suzuki–Miyaura coupling of bromoarenes with aryl boronic acids. The reactions were conducted under microwave irradiation at 160 °C using 12 mol% of Pd/CNS (0.36% actual Pd content). The reduction of nitroarenes into their respective amino compounds was achieved in 10–20 min (conversion up to 100%); by contrast, the Suzuki–Miyaura reactions yielded up to 98% at 150 °C with 10 mol% of Pd/CNS catalyst. The products were identified using gas chromatography and nuclear magnetic resonance spectroscopy. The catalyst was isolated from reaction mixture and reused without any significant loss in the activity. Thus, the present work introduces one-pot-derived porous CNSs as efficient catalytic support to Pd, establishing an alternative to existing Pd/C in terms of cost and efficiency.     

Sequential separation by HDEHP of carrier-free101,105,106Rh,103,104,105,106,110,112Ag and104,105,107,109,111Cd produced in alpha-particle activated palladium

Carrier free^101,105,106Rh,^{103,104,105,106,110,112}Ag and^{104,105,107,109,111}Cd radioisotopes were produced simultaneously by -particle irradiation of palladium target material in a variable energy cyclotron. The radioisotopes produced were extracted and separated from the activated target by LLX using HDEHP as liquid cation exchanger. With the help of -ray spectrometry the presence of several radioisotopes in the activated target matrix and their purity at each step of the separation was confirmed.     

Promising anticancer drug thapsigargin: A perspective toward the total synthesis

The guaianolide ring containing sesquiterpene thapsigargin is found in the roots and fruits of Mediterranean plant Thapsia garganica L. It is known for its activity as a potent antagonist for Ca²⁺-ATPase (sarco–endoplasmic reticulum Ca²⁺-ATPase) inhibition. Recently, a prodrug mipsagargin is being investigated to target the blood vessel of the cancer cells for the treatment of tumors. The limited natural supply (low isolation and only localized growth (Mediterranean area)) from the natural sources strongly urges for the development of chemical synthetic strategies to access these natural products. This review pertain the various strategies used so far in the thapsigargin’s synthesis, focusing on major contributions in the total synthesis till date.     

Isolation of dithiocarbazate salts as oxinato-complexes of titanium(IV), zirconium(IV) and hafnium(IV)

Summary Ionic chelate complexes of the type, [(⁵-R)₂ML][dtz] [R=cyclopentadienyl (Cp) or indenyl (C₉H₇); M=Ti^IV, Zr^IV or Hf^IV; HL=oxine; dtz=phenyldithiocarbazate (PhNHNHCS₂)] have been synthesised and characterised. Conductance measurements indicate that the complexes are 11 electrolytes. From i.r. and u.v. spectral studies we conclude that the oxinato-group is chelating. Consequently there is tetrahedral coordination around the metal ion.¹H and¹³C N.m.r. studies are consistent with the stoichiometries. X-ray powder diffraction studies have been made for [(⁵-Cp)₂ZrL][dtz]. For [(⁵-Cp)₂TiL][dtz] and [(⁵-Cp)₂ZrL][dtz] thermal (t.g. and d.t.a.) and mass spectral studies have been carried out.     

Bimetallic nanoparticles: a single step synthesis, stabilization, and characterization of Au-Ag, Au-Pd, and Au-Pt in sol-gel derived silicates

Nanobimetallic particles consisting of Au-Pd, Au-Ag, and Au-Pt have been synthesized in a single step by a sol-gel process and stabilized in liquid and solid matrices. Organically modified silicates (Ormosils) that play a dual role of a matrix and of a stabilizer have been used to obtain very stable dispersions in the form of sols, gels, and monoliths. The simultaneous reduction of metal ions leads to either a surface enriched with one component or an alloy type of structure depending on the bimetal combination. The nanometallic dispersions are characterized by absorbance, TEM, XRD, IR, XPS, and CO adsorption studies. The stabilized nanoparticles are found to be good electrocatalysts and the preliminary results on the electrochemical reduction of oxygen are reported.