Extraction-ability and -selectivity of tetra-aza-crown ethers for transition metal cations

In order to investigate the relative effects of the differences between the structures and lipophilicities of 1, 10-dioxa-4, 7, 13, 16-tetra-azacyclo-octadecane (TA-18-crown-6) and the tetrabenzyl derivative of 1,10-dioxa-4, 7, 13, 16-tetra-azacyclo-octadecane (TBTA-18-crown-6) on their extraction-abilities and -selectivities for transition metal cations, constants of the overall extraction (logK _ex) of 1:1 (M:L) complexes, the distribution (K _D) for two diluents (CH₂Cl₂ and CHCl₃) with different dielectric constants have been determined at 25 ± 0.1 °C. The magnitude of logK _ex is largely determined by that of K _D. The equilibrium constants of TA-18-crown-6 have been compared with those of TBTA-18-crown-6. It is found that:(i) logK _ex sequences of TA-18-crown-6 and TBTA-18-crown-6 for transition metals in CH₂Cl₂ lie in order: Fe³⁺ > Cu²⁺ > Mn²⁺ > Co²⁺ > Cd²⁺ > Ni²⁺ > Zn²⁺ and Fe³⁺ > Cu²⁺ > Co²⁺ > Mn²⁺ > Ni²⁺ > Cd²⁺ > Zn²⁺ respectively; (ii) the stability sequences of two types of tetra-aza-crown ethers with the transition metal cations in CHCl₃ are the same as follows: Fe³⁺ > Ni²⁺ > Cu²⁺ > Co²⁺ > Zn²⁺ > Cd²⁺ > Mn²⁺, and (iii) unusual selectivities are observed for transition metal-tetra-aza-crowns, e.g. the high Fe³⁺/M ⁿ⁺ selectivity factors (S_f) of TA-18-crown-6, except for the competitive-extractions for the special case in CHCl₃ of TBTA-18-crown-6, it was found that the Mn²⁺/M ⁿ⁺ values were relatively higher according to the other transition metal cations. A systematic sequence in these two types of solvents is not found for a given transition metal cation in terms of the variation of selectivity with the tetra-aza-crown ethers. The results provide alternatives for the rational design of other specific ligands on the transition metal cations.     

Erratum: Synthesis and characterization of diorganotin(IV) complexes of Schiff bases with ONO‐type donors and crystal structure of [N‐(2‐hydroxy‐4‐nitrophenyl)‐3‐ethoxysalicylideneiminato]diphenyltin(IV)

The article referenced above was first published online on 30 August 2007 with incorrect pagination; the pagination has now been corrected online and in print. Copyright © 2007 John Wiley & Sons, Ltd.     

Application of N,N‐bis(diphenylphosphino)aniline palladium(II) complexes as pre‐catalysts in Heck coupling reactions

Palladium(II) complexes with N,N‐bis(diphenylphosphino)aniline ligands catalyse the Heck reaction between styrene and aryl bromides, affording stilbenes in good yield. The structures of two of the complexes used as pre‐catalysts have been determined by single‐crystal X‐ray diffraction. Copyright © 2007 John Wiley & Sons, Ltd.     

Portfolio optimization in stochastic markets

We consider a multiperiod mean-variance model where the model parameters change according to a stochastic market. The mean vector and covariance matrix of the random returns of risky assets all depend on the state of the market during any period where the market process is assumed to follow a Markov chain. Dynamic programming is used to solve an auxiliary problem which, in turn, gives the efficient frontier of the mean-variance formulation. An explicit expression is obtained for the efficient frontier and an illustrative example is given to demonstrate the application of the procedure.     

Eigenvalues of Two Parameter Polynomial Operator Pencils of Waveguide Type

The spectral structure of two parameter unbounded operator pencils of waveguide type is studied. Theorems on discreteness of the spectrum for a fixed parameter are proved. Variational principles for real eigenvalues in some parts of the root zones are established. In the case of n = 1 (quadratic pencils) domains containing the spectrum are described (see Fig. 1–3). Conditions in the definition of the pencils of waveguide type arise naturally from physical problems and each of them has a physical meaning. In particular a connection between the energetic stability condition and a perturbation problem for the coefficients is given.     

Models for copper proteins. Copper(I) and (II) complexes of a novel binucleating tetraamino-tetrathioether ligand

The novel binucleating ligand, 6,6 prime-methylene-bis(5 prime-amino-3 prime,4 prime-benzo-2 prime-thiapentyl)-1,11-diamino-2,3:9,10-dibenzo-4,8-dithiaundecane (H4L) was prepared and reacted with copper(II) salts in dry MeOH to yield mixtures of copper(I) and copper(II) complexes with Cl- and ClO-4 counter ions. The amine functions on the ligand release protons to form copper(I) complexes: (Cu2L)X2, where X=Cl−, ClO4-. The complexes were oxidized to (Cu2L)X4 with H2O2 in DMF; Cu(NO3)2 gave a different complex, [Cu2(H4L)(NO3)2](NO3)2, as regards proton releasing ability, coordination and oxidation number. Evidence for the structures of this new tetraamino-tetrathioether ligand and its copper complexes is provided by 1H-, 13C-n.m.r., mass, u.v.–vis., i.r. spectra, elemental analyses, molar conductivities and magnetic moments. This revised version was published online in June 2006 with corrections to the Cover Date.     

Levels of natural and artifical radioactivity in sediments in the Eastern Black Sea of Turkey

Sediment samples collected from the Eastern Black Sea in 1993 from 15 sampling stations of different depths have been analyzed. Natural and artifical radionuclide activity levels in offshore sediment samples from the Eastern Black Sea in Turkey are reported about seven years after the Chernobyl accident. The purpose of this paper is to follow up the earlier study and present results for the distributions of radionuclides in sediments of the Black Sea.     

Optimization Strategy for Isocratic Separation of α-Aspartame and Its Breakdown Products by Reversed Phase Liquid Chromatography

α-Aspartame (L-α-aspartyl-L-phenylalanine methyl ester) is increasingly being used in wide variety of commonly consumed food products. This structure contains ester and peptide bonds. The ester linkage may hydrolyze to produce L-α-aspartyl-L-phenylalanine or cyclohydrolyze to produce the corresponding diketopiperazine ring. This ring can open to form L-α-aspartyl-L-phenylalanine and ultimately this compound can hydrolyze to L-phenylalanine and L-aspartic acid. The pH, buffer type, concentration, the presence of water and temperature are other important factors affecting its stability. Because α-aspartame can lose its sweetness under these conditions determination of aspartame and its breakdown products is extremely important for diet foods quality. The optimum mobile phase for the chromatographic separation was found to be acetonitrile-water (20:80, ν/ν) with 5.10^?3 M hexanesulfonic acid and a pH of 2.6.     

Measurement of absolute intensity of 1001 keV gamma-ray of 234mPa

The sorption behavior of ²³⁵U fission fission products ⁹⁹Mo and ¹³²Te was studied through batch and dynamic experiments when they were dissolved in 1 to 7M HNO₃ solutions. It was found that ⁹⁹Mo is always totally adsorbed on hydrated SnO₂, while ¹³²Te is rather weakly adsorbed, therefore they can be separated from each other although ¹³²Te in the solution still remains contaminated with other radionuclides as well as ⁹⁹Mo does in the solid.