Removal of cesium and strontium from acid solution using a composite of zirconium molybdate and zirconium tungstate

A composite mixture of zirconium molybdate and zirconium tungstate was prepared and studied for the sorption of cesium and strontium as a function of nitric acid, metal ion concentration, time and temperature. The distribution coefficient (K_d) of 7000 ml/g (~90% sorption) and 70 ml/g (~20% sorption) was obtained for the sorption of cesium and strontium in 0.1M nitric acid, respectively. Experimental sorption capacity, b for cesium was found to be 50 mg/g from 0.1M HNO₃ and 30 mg/g for strontium from 0.001M nitric acid. The sorption of strontium on the sorbent was accompanied by the absorption of heat but the sorption of Cs⁺ results in the liberation of heat. Column studies were conducted by following a breakthrough (BT) curve of cesium and strontium up to C/C₀=1 and the results are reported.     

Solvent polarity driven helicity inversion and circularly polarized luminescence in chiral aggregation induced emission fluorophores

Development of functional materials capable of exhibiting chirality tunable circularly polarized luminescence (CPL) is currently in high demand for potential technological applications. Herein we demonstrate the formation of both left- and right-handed fluorescent helical superstructures from each enantiomer of a chiral tetraphenylethylene derivative through judicious choice of the solution processing conditions. Interestingly, both the aggregation induced emission active enantiomers exhibit handedness inversion of their supramolecular helical assemblies just by varying the solution polarity without any change in their molecular chirality. The resulting helical supramolecular aggregates from each enantiomer are capable of emitting circularly polarized light, thus enabling both right- and left-handed CPL from a single chiral material. The left- and right-handed supramolecular helical aggregates in the dried films have been characterized using spectroscopy, scanning electron microscopy, and transmission electron microscopy techniques. These new chiral aggregation induced emission compounds could find applications in devices where CPL of opposite handedness is required from the same material and would facilitate our understanding of the formation of helical assemblies with switchable supramolecular chirality.

The formation of both left- and right-handed helical superstructures with circularly polarized luminescence has been achieved in a chiral tetraphenylethylene derivative just by varying the solution polarity without any change in molecular chirality.     

Mass spectra of aliphatic dicarboxylic acids and their dimethyl esters: Cyclic structures for the [M − H2O]+˙ ions from the diacids and [M − MeOH]+˙ ions from the dimethyl esters

Methyl 2-oxocycIoalkane carboxylate structures are proposed lor the [M ? MeOH]^+˙ ions from dimethyl adipate, pimelate, suberate and azelate. This proposal is based on a comparison of the metastable ion mass spectra and the kinetic energy releases for the major fragmentation reaction of these species with the same data for the molecular ions of authentic cyclic β-keto esters. The mass spectra of α,α,α′,α′-d₄-pimelic acid and its dimethyl ester indicate that the α-hydrogens are involved only to a minor extent in the formation of [M ? ROH]^+˙ and [M ? 2ROH]^+˙ ions, while these α-hydrogens are involved almost exclusively in the loss of ROH from the [M ? RO˙]⁺ ions (R = H or CH₃). The molecules XCO(CH₂)₇COOMe (X = OH, Cl) form abundant ions in their mass spectra with the same structure as the [M ? 2MeOH]^+˙ ions from dimethyl azelate.     

Palladium(0)-catalyzed cascade one-pot synthesis of isoxazolidines

A highly diastereoselective cascade reaction protocol has been developed for the synthesis of isoxazolidine derivatives utilizing aryl halides, O-homoallyl hydroxylamine and palladium(0) in a one-pot reaction.     

Enhanced photoactivity of neodymium doped mesoporous titania synthesized through aqueous sol–gel method

Nanosize neodymium doped titania has been prepared by hydrolysis of titanium oxychloride followed by peptisation under acidic condition. The anatase to rutile phase transformation temperature was found to increase by 150 °C as a result of neodymium doping. The doped sample shows 10 times higher surface area than the undoped one after calcining at 700 °C. All the samples calcined at 500, 600 and 700 °C show type IV isotherm, which is characteristic of mesoporous material. The pore size distribution curves also show that the pores are in mesoporous region. Further, the neodymium doped titania shows increased photoactivity than the undoped titania with respect to decomposition of methylene blue when subjected to UV light. The transmission electron micrograph indicates that a nanocrystalline doped titania is obtained through the present method. The effect of neodymium doping on the anatase phase stability, specific surface area and photoactivity are reported.     

Studies in fluorinated 1,3-diketones and related compounds Part XII. Synthesis and spectroscopic studies of some new polyfluorinated 1,3-diketones,and their copper 1,3-diketonates

New polyfluorinated 1,3-diketones have been prepared from polyfluorinated acetophenones and appropriate esters in the presence of sodamide. The corresponding copper 1,3-diketonates have been obtained by treating a methanolic solution of polyfluorinated 1,3-diketone with methanolic solution of copper acetate. The polyfluorinated 1,3-diketones have been characterized by elemental as well as by spectral studies, viz: I.R., ¹H N.M.R. and ¹⁹F N.M.R. In I.R., characteristic absorptions observed are: CF stretching bands (1300 ? 1000) cm^?1, CF deformation modes (900 ? 700 cm^?1) and intramolecular hydrogen bonding (3000 ? 2500 cm^?1). In ¹H N.M.R. methine ( = C$\text{H}$) signal is observed at δ 6.2 ? 6.8 ppm and enolic proton resonance signal at δ 13 ? 15 ppm indicating the presence of strong hydrogen bonding in such polyfluorinated 1,3-diketones.     

Preconcentration and speciation of inorganic and methyl mercury in waters using polyaniline and gold trap-CVAAS

Applicability of polyaniline (PANI) has been investigated for the preconcentration and speciation of inorganic mercury (Hg²⁺) and methyl mercury (CH₃Hg⁺) in various waters (ground, lake and sea waters). Preliminary experiments (batch) with powdered PANI for the quantitative removal of both Hg²⁺ and CH₃Hg⁺ showed that the retention of Hg²⁺ was almost independent of pH while a pH dependent trend from pH 1 to 12 was seen for CH₃Hg⁺ with maximum retention at pH > 5. Time dependence batch studies showed that a contact time of 10 min was sufficient to reach equilibrium. The K_d values were found to be ∼8 × 10⁴ and ∼7 × 10³ for Hg²⁺ and CH₃Hg⁺, respectively.Subsequently column experiments were carried out with PANI and the separation of the species was carried out by selective and sequential elution with 0.3% HCl for CH₃Hg⁺ and 0.3% HCl-0.02% thiourea for Hg²⁺. This was then followed by further pre-concentration of mercury on a gold trap and its determination by CVAAS. The uptake efficiency studies showed that the PANI column was able to accumulate up to 100 mg Hg²⁺/g and 2.5 mg CH₃Hg⁺/g. This method allows both preconcentration and speciation of mercury with preconcentration factors around 120 and 60 for Hg²⁺ and CH₃Hg⁺, respectively. The interfering effects of various foreign substances on the retention of mercury were investigated.     

Kinetics and mechanism of oxidation of some reducing sugars by diperiodatoargentate(III) in alkaline medium

Summary The kinetics of oxidation of d-glucose, d-galactose, d-fructose, d-ribose, d-arabinose, d-xylose and 2-deoxyd-glucose by diperiodatoargentate(III) (DPA) have been investigated in alkaline medium. The order of the reaction with respect to [DPA] is unity while the order with respect to [sugar] is < 1 over the concentration range studied. The rate increases with an increase in [OH ^–] and there is a marginal decrease in the rate with an increase in [IO _inf4 ^sup– ]. No significant dependence on ionic strength was found, but the rate increases with a decreasing dielectric constant. Formic acid and the corresponding aldonic acids were detected as the products of oxidation. The participation of the open chain form of the sugar and a mechanism involving the initial formation of a complex between the enediol of the sugar and Ag^III are proposed.     

Oxidation of cobalt(II) aminopolycarboxylate complexes by peroxomonophosphoric acid in acetate buffers. A kinetic study

Summary The kinetics of oxidation of the Co^II complexes [Co(edta)]^2– and [Co(hedta)]^– [H₄edta=ethylenediamine tetraacetic acid and H₃hedta=N-(2-hydroxyethyl)ethylenediamineN, N, N triacetic acid] by peroxomonophosphoric acid (PMPA) in acetate buffer were investigated spectrophotometrically. The reactions exhibit first order behaviour in each reactant and are markedly in hibited by H⁺. A plausible mechanism consistent with the observed results is proposed.     

Oxidation of divalent manganese by peroxodiphosphate in acetate buffers. A kinetic study

Bivalent manganese in oxidized to the tervalent state in 4.0–5.3 pH (acetate buffers) when treated with an excess of peroxodiphosphate (PDP). Kinetic evidence for the formation of a 11 complex between manganese(II) and PDP was obtained. The reaction exhibits first order dependence on [Mn(II)] and fractional order dependence on [PDP]. The reaction is markedly inhibited by H⁺ ions. A plausible mechanism consistent with the observed data is proposed.

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pH=4,0–5,3 (). (II) 11. [Mn(II)] []. H⁺ . , .