Neuere Entwicklungen der flammenphotometrischen Analysenverfahren

Zusammenfassung Es wird gezeigt, daß man durch Einsatz von reduzierenden Flammen, durch Einsatz von Chemiluminescenzvorgängen in Flammen, durch Atomabsorptionsverfahren, durch Modulations- und Differentiations-operationen eine Reihe von weiteren Elementen mit den schnellen und spezifischen Flammenmethoden analytisch gut erfassen kann. Hierbei wird insbesondere auf die Bestimmung von Spurenelementen in Mikroproben mit möglichst einfachen Mitteln eingegangen.

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Summary It is demonstrated that one can grasp analytically well a series of further elements with the quick and specific flame methods by use of chemiluminescence processes in flames, by atomic absorption methods, by operations of modulation and differentiation. Hereby the determination of trace elements is specifically treated in microprobes with the most possible simple means.

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Unterstützt mit Mitteln der Deutschen Forschungsgemeinschaft.

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Herrn Prof. Dr. Bohnstedt zum 65. Geburtstag gewidmet.

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Meinen Mitarbeitern, insbesondere Herrn Dipl. Phys. W. Lang und Frau B. Gutsche, die an den zuletzt besprochenen Ergebnissen einen maßgeblichen Anteil hatten, als auch der Deutschen Forschungsgemeinschaft sei an dieser Stelle herzlichst gedankt.     

Determination of gallium in biological fluids using inductively coupled plasma mass spectrometry

A procedure for the determination of gallium in biological fluids by inductively coupled plasma mass spectrometry was developed. The detection limits of gallium calculated from the 3s value were 60 ng/L for urine, 32 ng/L for a model solution of intestinal juice, and 50 ng/L for serum. The accuracy of the procedure was tested using a standard addition method. The nature of a background signal on the masses of gallium isotopes was studied with the use of a high-resolution mass spectrometer, and the background concentration of gallium in biological fluids was evaluated (5–7 ng/L). It was found that a background level in measurements performed on a quadrupole mass spectrometer depends on the interfering influence of polyatomic ions with close m/z ratios rather than on the background concentration of gallium. The procedure makes it possible to study the stability of pharmaceutical preparations based on gallium in biological media, their metabolism, and the excretion of preparations from the body.     

A Convenient Synthesis of Hydrophenanthrenes the Synthesis of Ferrugindl and Xanthoperol

We wish to report an approach (equation 1) to hydrophenanthrenes which shows considerable promise of providing a general synthetic route for diterpenes, steroids, triterpenes, and tetraterpenes. Herein we illustrate the utility of this Friedel-Crafts type of procedure^3,6 by describing a synthesis of ferruginol (6) ⁷ and xanthoperol (8).⁸     

Radiation-initiated synthesis of tetrafluoroethylene telomers in 1,2-dibromotetrafluoroethane at a constant pressure of the monomer in the reactor

The kinetics of radiation-initiated telomerization of tetrafluoroethylene in a 1,2-dibromotetrafluoroethane solution at a constant concentration (pressure) of the monomer in the reactor was studied. The properties, molecular structure, and morphology of the telomers were studied by IR spectroscopy, scanning electron microscopy, and elemental and thermal gravimetric analyses. The synthesized telomers show promise for the development of fluoropolymeric nanocomposites and protective hydrophobic and antifriction coatings.     

Near-Enantiopure Trimerization of 9-Ethynylphenanthrene on a Chiral Metal Surface

Enantioselectivity in heterogeneous catalysis strongly depends on the chirality transfer between catalyst surface and all reactants, intermediates, and the product along the reaction pathway. Herein we report the first enantioselective on-surface synthesis of molecular structures from an initial racemic mixture and without the need of enantiopure modifier molecules. The reaction consists of a trimerization via an unidentified bonding motif of prochiral 9-ethynylphenanthrene (9-EP) upon annealing to 500 K on the chiral Pd₃-terminated PdGa{111} surfaces into essentially enantiopure, homochiral 9-EP propellers. The observed behavior strongly contrasts the reaction of 9-EP on the chiral Pd₁-terminated PdGa{111} surfaces, where 9-EP monomers that are in nearly enantiopure configuration, dimerize without enantiomeric excess. Our findings demonstrate strong chiral recognition and a significant ensemble effect in the PdGa system, hence highlighting the huge potential of chiral intermetallic compounds for enantioselective synthesis and underlining the importance to control the catalytically active sites at the atomic level.     

Rare-earth Metal Borosilicides R9Si15–xB3 (R = Tb,Yb): New Ordered Structures Derived from the AlB2 Structure Type

Two novel ternary borosilicides R₉Si_15–xB₃ (R = Tb, x = 1.80, R = Yb, x = 1.17) were synthesized from the initial elements using tin flux method. Their crystal structures were determined by means of X-ray single crystal diffraction. Both refer to space group R32, Z = 1: a = 6.668(2) Å, c = 12.405(4) Å [R₁ = 0.027, wR₂ = 0.031 for 1832 reflections with I_o > 2σ (I_o)] for Tb₉Si_15–xB₃, and a = 6.5796(3) Å, c = 12.2599(5) Å [R_F = 0.052, wR = 0.090 for 1369 reflections with I_o > 2σ (I_o)] for Yb₉Si_15–xB₃. The structures represent a new structure type, derived from that of AlB₂, with ordering in the metalloid sublattice resulting in distorted [Si₅B] hexagons. The presence or absence of boron in this ordered structure is discussed on the basis of difference Fourier syntheses, interatomic distances, structural analysis, and theoretical calculations in relation with the parent structures of the binaries AlB₂ and Yb₃Si₅ (Th₃Pd₅ type of structure). Theoretical calculations show substantial covalent interactions between the metal and nonmetal elements. The small percentage of silicon atoms, which are missing in these nonstoichiometric compounds, probably allows strengthening boron-metal and boron-silicon bonding.     

Reactive polymers incorporating silyl enol ether groups. I. synthesis by radical polymerization of 2-(trimethylsiloxy)-butadiene and 2-(tert)-butyldimethylsiloxy butadiene

2-(Trimethylsiloxy)butadiene (TMSBD) and 2-(tert-butyldimethylsiloxy)butadiene (TBMSBD) were copolymerized with styrene (St) and methyl methacrylate (MMA) under free-radical conditions. The obtained polymers were found to contain reactive silyl enol ether groups in a ratio identical to the TMSBD or TBMSBD molar fraction in the copolymer. All investigated samples displayed only 1,4- and 3,4-microstructures. The influence of several experimental factors on the yields, rates of polymerization, microstructures, and copolymer compositions were examined. Monomer reactivity ratios r₁ and r₂ at 60°C were determined from copolymer composition curves at low conversions. The homopolymerization of TBMSBD was also investigated and results were compared with those previously obtained for TMSBD. A slight increase in rates was observed and was rationalized on the basis of the higher viscosity resulting from the structural change in the monomer. Thermal stabilities of the synthesized polymers were investigated by TGA and their glass transition temperatures were determined by DSC. All measurements are compatible with a possible use of TMSBD and TBMSBD copolymers as reactive polymers. © 1996 John Wiley & Sons, Inc.     

Lichtblicke – Petrischalenexperimente in der Overhead-Projektion

Overhead projection with supplementary lenses provides „wallfilling big screen”︁ detailed pictures of physical and chemical phenomena and thus helps to train chemists to make accurate observations, comparisons, and interpretations. By using divided petri dishes, it is possible to present parallel and control experiments with minimal amounts of substances in one field of vision, and thus to establish the links between substance and reaction, and formula and equation. In particular, for the demonstration of electrochemical processes, the divided petri dish proves to be a projectable minimal system, which is characterized by maximum economy and ecology. Great recognition with little substance?.