Synthesis,spectroscopic characterization and redox properties of titanium and vanadium substituted Keggin-type heteropolyanions

The Ti-substituted heteropolytungstates K7[TiIVW11–BO40] and K6[VVTiIVW10PO40] have been synthesized and characterized by elemental analyses and spectroscopic techniques. Their redox properties have been studied by cyclic voltammetry, and the compounds were found to be more difficult to reduce than the unsubstituted heteropolyanion. The one- and two-electron reduced heteropoly blues of [VVTiIVW10PO40]6–, namely [VIVTiIVW10PO40]7– and [VIVTiIIIW10PO40]8–, have also been prepared by chemical methods. Their optical spectra show low-energy intervalence charge-transfer bands as well as the expected d–d transitions. The optical and e.s.r. investigations indicate that VIV and TiIII are not vicinal in [VIVTiIIIW10PO40]8–.     

Photoinduced Copper‐Catalyzed Regioselective Synthesis of Indoles: Three‐Component Coupling of Arylamines,Terminal Alkynes,and Quinones

The first successful example of a visible‐light‐induced copper‐catalyzed process for C H annulation of arylamines with terminal alkynes and benzoquinone is described. This three‐component reaction allows use of a variety of commercial terminal alkynes as coupling partners for the one‐step regioselective synthesis of functionalized indoles. Moreover, the current process represents a sustainable and atom‐economical approach for the preparation of complex indoles from easily accessible starting materials under visible‐light irradiation, without the need for expensive metals and harsh reaction conditions.     

Performance of immobilized moss in the removal of 137Cs and 90Sr from actual low-level radioactive waste solutions

The efficiency of immobilized moss as a bio-sorbent for the removal of ¹³⁷Cs and ⁹⁰Sr radionuclides from actual low-level radioactive waste (LLW) solutions was investigated. Preliminary batch experiments with the moss (Funaria hygrometrica) for the sorption of Cs and Sr have shown a pH dependent binding trend from pH 1–13, with maximum binding between pH 5–10. Time dependence of the batch studies showed that a contact time of 30 minutes was sufficient to reach equilibrium. Column experiments for the sorption of Cs and Sr by moss after immobilizing in polymer silica matrix demonstrated that the sorbent is capable of removing considerable amounts of Cs and Sr from actual LLW solutions under constant flow conditions. The adsorption capacity was estimated to be 8.5 mg/g for Cs and 15 mg/g for Sr. These sorbed metal ions from the column could be leached out using 0.20M nitric acid. The regenerated sorbent exhibited relatively the same initial binding capacity of both Cs and Sr even after 3 cycles of reuse. This revised version was published online in July 2006 with corrections to the Cover Date.     

Magnetic field induced donor exciton binding energy in a strained InAs/InP quantum wire

Magneto–exciton bound donor is investigated in a strained InAs/InP quantum wire within the framework of single band effective mass approximation. The strain contribution to the potential is determined via deformation potential theory. The interband optical transition is computed with the various structural parameters in the influence of magnetic field.     

Synthesis,CMC Determination,Antimicrobial Activity and Nucleic Acid Binding of A Surfactant Copper(II) Complex Containing Phenanthroline and Alanine Schiff-Base

A new water-soluble surfactant copper(II) complex [Cu(sal-ala)(phen)(DA)] (sal-ala = salicylalanine, phen = 1,10-phenanthroline, DA = dodecylamine), has been synthesized and characterized by physico-chemical and spectroscopic methods. The critical micelle concentration (CMC) values of this surfactant–copper(II) complex in aqueous solution were obtained from conductance measurements. Specific conductivity data (at 303, 308, 313. 318 and 323 K) served for the evaluation of the temperature-dependent CMC and the thermodynamics of micellization (ΔG⁰m, ΔH⁰m and ΔS⁰m). The interaction of this complex with nucleic acids (DNA and RNA) has been explored by using electronic absorption spectral titration, competitive binding experiment, cyclic voltammetry, circular dichroism (CD) spectra, and viscosity measurements. Electronic absorption studies have revealed that the complex can bind to nucleic acids by the intercalative binding mode which has been verified by viscosity measurements. The DNA binding constants have also been calculated (K_b?=?1.2?×?10⁵ M^?1 for DNA and K_b?=?1.6?×?10⁵ M^?1 for RNA). Competitive binding study with ethidium bromide (EB) showed that the complex exhibits the ability to displace the DNA-bound-EB indicating that the complex binds to DNA in strong competition with EB for the intercalative binding site. The presence of hydrophobic ligands, alanine Schiff-base, phenanthroline and long aliphatic chain amine in the complex were responsible for this strong intercalative binding. The surfactant–copper (II) complex was screened for its antibacterial and antifungal activities against various microorganisms. The results were compared with the standard drugs, amikacin(antibacterial) and ketokonazole(antifungal).     

Mechanism of selective oxidation of organic sulfides with Oxo(salen)chromium(V) complexes

The selective oxidation of organic sulfides to sulfoxides by oxo(salen)chromium(V) complexes in acetonitrile is overall second-order, first-order each in the oxidant and the substrate. The rate constant, k(2), values of several para-substituted phenyl methyl sulfides correlate linearly with Hammett sigma constants and the rho values are in the range of -1.3 to -2.7 with different substituted oxo(salen)chromium(V) complexes. The reactivity of different alkyl sulfides is in accordance with Taft's steric substituent constant, E(S). A mechanism involving direct oxygen atom transfer from the oxidant to the substrate rather than electron transfer is envisaged. Correlation analyses show the presence of an inverse relationship between reactivity and selectivity in the reaction of various sulfides with a given oxo(salen)chromium(V) complex and vice versa. Mathematical treatment of the results shows that this redox system falls under strong reactivity-selectivity principle (RSP).     

SCF molecular orbital studies of internal rotation in the monofluorobenzaldehydes

The potential function for internal rotation of the aldehyde group in the orthometa- and para-fluorobenzaldehydes is calculated by CNDO/2, INDO and STO/6G methods, assuming invariant bond lengths. The INDO and STO/6G calculations indicate the equilibrium geometry to be essentially planar and the barrier to internal rotation to be the potential energy of the molecule when the plane of the aldehyde group is perpendicular to the ring plane; CNDO/2 leads to different conclusions, however. Relative stabilities of O-cis and O-trans rotamers of the planar configuration are discussed. Comparisons are made with the V barriers and the enthalpies of activation as determined by the dielectric absorption method using a matrix technique.     

Binuclear Cu(II) chiral complexes: synthesis,characterization and application in enantioselective nitroaldol (Henry) reaction

Enantiopure macrocyclic ligands were synthesized from (1R,2R)‐(+)‐ and (1S,2S)‐(?)‐diphenylethylenediamine with 3,3'‐methylenebis(5‐(tert‐butyl)‐2‐hydroxybenzaldehyde) and characterized. The chirality transfer and chiral inversion from ligand to copper(II) metal centre were studied using circular dichroism spectroscopy. The enantiopure binuclear copper(II) complexes (ΔΔ and ΛΛ) were used as catalysts for asymmetric nitroaldol reaction to generate β‐nitroalcohol with 88% yield and 67% enantioselectivity. Copyright © 2015 John Wiley & Sons, Ltd.