Neue Rheniumkomplexe mit Trichalkogenido- und Tetrachalkogenido-Chelatliganden

New Rhenium Complexes Containing Trichalcogenido and Tetrachalcogenido Chelate Ligands The reactions of Cp*ReCl₄ with polychalcogenide salts such as Na₂S₄ or (NEt₄)₂Se₆ lead initially to the violet trichalcogenido chelate complexes Cp*ReCl₂(E₃) (E = S ( 3a ), Se ( 3b )) which, due to their functional chloro ligands, can be used as intermediates for further reactions. Upon hydrolysis in moist solvents or aminolysis with tert. butylamine 3a, b are converted into the tetrachalcogenido chelate complexes Cp*Re(O)(E₄) (E = S ( 4a ), Se ( 4b )) and Cp*Re(N^tBu)(E₄) (E = S ( 5a ), Se ( 5b )), respectively. X-Ray structure analyses were carried out for the three mononuclear cyclo-oligoselenido compounds 3b–5b . It appears that the size of the Se^2?_n chelate ring (n = 3 or 4) essentially depends on steric factors within the coordination sphere of rhenium.     

The Molybdenum Stannide MoSn2

The title compound was prepared by annealing molybdenum powder with an excess of tin. Single-crystals were obtained by dissolving the tin-rich matrix in hydrochloric acid. They are Pauli paramagnetic. The crystal structure was determined from single-crystal X-ray diffractometer data: P6₂22, a = 548.8(1) pm, c = 1417.1(2) pm, Z = 6, R = 0.036 for 18 variable parameters and 389 structure factors. MoSn₂ is only the second representative of the hexagonal Mg₂Ni-type structure. The relation of the structure to the CuAl₂-type is discussed.     

Studies on the elimination of sulfide interference in the potentiometric determination of chloride using ion selective electrodes in a flow injection system

Detailed investigations have been reported on the application of a common procedure using bromate in nitric acid for the removal of the interference of sulfide in the direct potentiometric determination of chloride using silver-based ion selective electrodes in a flow injection system. It is shown that this procedure is not very efficient and carries a high risk of chloride underestimation. With increasing levels of sulfide the oxidation of chloride to elemental chlorine becomes progressively significant and under certain circumstances virtually no chloride is left irrespective of its initial concentration. Hydrogen peroxide in alkaline medium is proposed as a suitable alternative for the efficient removal of sulfide without any adverse effects on the potentiometric method.     

AUTOMATED MECHANICAL STIMULATION AND MEASUREMENT OF BIOLUMINESCENCE IN MARINE DINOFLAGELLATES

A new integrated system for reproducible, automated mechanical stimulation and measurement of bioluminescence (BL) in multiple samples of marine dinoflagellate cell suspensions is described. The system was designed to allow the application of standardized experimental routines to parallel test vials for the purpose of toxicity testing. A sample tray delivered test vials to the position of mechanical stimulation and BL measurement. Mechanical stimulation of BL was applied as sharp rotation-onset of the test vial about its vertical axis. Thus, any direct chemical or physical perturbation of the cell suspension was avoided. A silicon photovoltaic cell measured the emitted light. Stimulation, measurement and recording of BL were integrated and controlled by specially developed software, which runs on a personal computer in the graphic environment of MS-Windows. Precise scheduling, flexible programming and identical repetition of experimental routines are possible in practice. For Gonyaulax polyedra, details of BL, as stimulated and measured with the new system, are presented and discussed. We conclude that the system exhibits specific features that offer wide potential of application in several fields of research on dinoflagellate BL, particularly for toxicity testing.     

Applications of adsorptive stripping voltammetry for the trace analysis of metals, pharmaceuticals and biomolecules

 A review with 159 references is presented on the applications of adsorptive stripping voltammetry (AdSV) for determining trace metal ions in different environmental samples (e.g. water, soil, plant, biological fluids). The analytical applications of AdSV to biologically active organic compounds (e.g. pharmaceuticals, pesticides, biomolecules) are also discussed. Received: 18 December 1995/Revised: 8 January 1997/Accepted: 12 January 1997     

Chloroselenate mit zwei- und vierwertigem Selen: 77Se-NMR-Spektren,Synthese und Kristallstrukturen von (PPh4)2SeCl6 · 2 CH2Cl2, (NMe3Ph)2SeCl6, (K-18-Krone-6)2SeCl6 · 2 CH3CN,PPh4Se2Cl9, (NEt4)2Se2Cl10, (PPh4)2Se3Cl8 · CH2Cl2 und (PPh4)2Se4Cl12 · CH2Cl2

Chloroselenates with Di- and Tetravalent Selenium: ⁷⁷Se-NMR-Spectra, Syntheses, and Crystal Structures of (PPh₄)₂SeCl₆ · 2 CH₂Cl₂, (NMe₃Ph)₂SeCl₆, (K-18-crown-6)₂SeCl₆ · 2 CH₃CN, PPh₄Se₂Cl₉, (NEt₄)₂Se₂Cl₁₀, (PPh₄)₂Se₃Cl₈ · CH₂Cl₂, and (PPh₄)₂Se₄Cl₁₂ · CH₂Cl₂ The title compounds were obtained from reactions of selenium and selenium tetrachloride with PPh₄Cl, NEt₄Cl, NMe₃PhCl, or (K-18-crown-6)Cl in dichloromethane or acetonitrile. (PPh₄)₂Se₃Cl₈ · CH₂Cl₂ was also formed from GeSe, PPh₄Cl and chlorine in acetonitrile. The ⁷⁷Se-NMR spectra of the solutions show the presence of dynamical equilibria which, depending on composition, mainly contain SeCl₂, SeCl₄, Se₂Cl₂, SeCl₆^2–, Se₂Cl₆^2–, and/or Se₂Cl₁₀^2–. Solutions of AsCl₃ and (PPh₄)₂Se₄ in acetonitrile upon chlorination with Cl₂ or PPh₄AsCl₆ yielded (PPh₄)₂Se₂Cl₆, while (PPh₄)₂As₂Se₄Cl₁₂ was the product after chlorination with SOCl₂. According to the X-ray crystal structure analyses the ions SeCl₆^2–, Se₂Cl₉^–, and Se₂Cl₁₀^2– have the known structures with octahedral coordination of the Se atoms. The structure of the Se₃Cl₈^2– ion corresponds to that of Se₃Br₈^2– consisting of three SeCl₂ molecules associated via two Cl^– ions. (PPh₄)₂Se₄Cl₁₂ · CH₂Cl₂ is isotypic with the corresponding bromoselenate and contains anions in which three SeCl₂ molecules are attached to a SeCl₆^2– ion; there is a peculiar Se–Se interaction.     

The interaction of cationic polymers with human hair

We present a combination of electrochemical methods, i.e. polyelectrolyte titration and streaming potential measurement, and AFM to characterise the adsorption and desorption behaviour and the morphology of a set of polyquaternium polymers on human hair. Specific charge density and molar mass are correlated to the amount of adsorbed polymer and the ease of desorption. Results are in line with a simple model of coulombic interaction between hair and polymer and are interpreted on this basis.     

Enzyme Catalysis “Reilluminated”

In a new light : The NADPH:protochlorophyllide (Pchlide) oxidoreductase (POR; see structure, green Pchlide, yellow NADPH) is a good model to investigate catalytical processes in enzymes, as its light activation allows an immediate start of the catalyzed reaction. By irradiation with weak, short laser pulses it is possible to detect conformation changes during the reaction and thus to uncover the elementary steps of the catalytic process.