Untersuchung einer Methode zur Bestimmung von Blei, Cadmium, Quecksilber, Arsen und Tellur in Lebensmitteln mit Hilfe der R?ntgenfluorescenzanalyse

Zusammenfassung Der Aufschluß von Nahrungsmitteln tierischen Ursprungs mit Salpetersäure-Schwefelsäure in einer Polyäthylenflasche bei 60° C und mit Salpetersäure in einem Bombengefäß bei 150° C wurde untersucht. Beide Verfahren liefern befriedigende Ergebnisse. Im zweiten Fall besteht wegen kleinerer Reagensmengen jedoch eine geringere Gefahr des Einschleppens von Blindwerten. Blei, Cadmium und Quecksilber können aus der Aufschlußlösung durch Adsorption an dem Austauscherharz Chelex 100 oder durch Fällung mit Ammonium-pyrrolidindithiocarbamat unter Zusatz von Kupfer als Träger abgetrennt werden. Arsen und Tellur lassen sich anschließend zusammen mit Kupferträger durch Schwefelwasserstoff ausfällen. Die Ausbeuten für Aufschluß und Abtrennung liegen bei 90% oder darüber. — Die quantitative Bestimmung wurde mit Hilfe der energiedispersiven Röntgenfluorescenzanalyse durchgeführt, wobei ¹⁰⁹Cd bzw. ²⁴¹Am oder eine Röntgenröhre mit Zirkon oder Molybdän als Sekundärstrahler zur Anregung verwendet wurden. Beim Blei und Quecksilber konnten noch 1 g, beim Arsen und Tellur noch 0,5 g quantitativ bestimmt werden.

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Investigation of a method for the determination of lead, cadmium, mercury, arsenic and tellurium in food by means of X-ray fluorescence analysis

The decomposition of food of animal origin with a mixture of nitric acid and sulphuric acid in a polyethylene flask at 60° C and with nitric acid in a steel vessel at 150° C was investigated. Both procedures give satisfactory results. The advantage of the second procedure lies in the small amounts of reagents needed, thus keeping blank values low. Lead, cadmium and mercury can be separated from the decomposition solution by the chelating resin Chelex 100 or by precipitation with ammonium pyrrolidine dithiocarbamate, using copper as carrier. Arsenic and tellurium may be precipitated in the filtrate by hydrogen sulphide, using copper as carrier. The overall yields are about 90% or more. — The quantitative determination was performed by means of the energy dispersive X-ray fluorescence analysis, using ¹⁰⁹Cd or ²⁴¹Am sources or an X-ray tube with zirconium or molybdenum as secondary target for the excitation. 1 g of lead and mercury and 0.5 g of arsenic and tellurium could still be determined.

     

New Perspectives in Polyoxometalate Chemistry by isolation of compounds containing very large moieties as transferable building blocks: (NMe4)5[As2Mo8V4AsO40] · 3H2O, (NH4)21[H3Mo57V6(NO)6O183(H2O)18] · 65 H2O, (NH2Me2)18(NH4)6[Mo57V6(NO)6O183(H2O)18] · 14 H2O,and (NH4)12[Mo36(NO)4O108(H2O)16] · 33 H2O

The compounds (NMe₄)₅[As₂Mo₈V₄AsO₄₀] · 3 H₂O 2a , (NH₄)₂₁[H₃Mo₅₇V₆(NO)₆O₁₈₃(H₂O)₁₈] · 65 H₂O 3a , (NH₂Me₂)₁₈(NH₄)₆[Mo₅₇V₆(NO)₆O₁₈₃(H₂O)₁₈] · 14 H₂O 3b and (NH₄)₁₂[Mo₃₆(NO)₄O₁₀₈(H₂O)₁₆] · 33 H₂O 4a ( 3a and 4a were not correctly reported in the literature regarding to their composition, structures and the oxidation states of the metal centres) which contain large isolated anionic species, have been prepared (among them 3a, 3b , and 4a in rather high yield) and characterized by complete crystal structure analysis as well as IR/Raman, UV/VIS/NIR, ESR spectroscopy and magnetic susceptibility measurements, redox titrations, bond valence sum calculations, elemental analyses and thermogravimetric studies. Perspectives for polyoxometalate chemistry referring to the synthesis of “extremely” large nanoscaled species are discussed, together with the occurrence of a large transferable {Mo₁₇} building block in the compounds 3a, 3b and 4a which also exists in the corresponding iron compound Na₃(NH₄)₁₂[H₁₅Mo₅₇Fe₆(NO)₆O₁₈₃(H₂O)₁₈] · 76 H₂O 7a .     

Synthesis of Stereochemically Flexible Cyclic Biphenylbisphosphinite Ligands: Control of the Dynamics and Selectivity

Novel l -tartaric acid based stereodynamic biphenylbisphosphinite ligands with anilino linkers were prepared as cyclic diamide compounds. The influence of the constitutional substitution pattern of the amino group at the aniline moiety on the diastereoselective formation of the ligand was investigated. While the meta-anilino bridged ligands showed a highly dynamic behavior and no discrimination between (R_ax) and (S_ax) configuration, l -tartaric acid substitution on ortho-anilino bridged ligands leads to diastereoselective self-alignment of the central biphenol axis, which controls the stereoselectivity of the ligand and catalyst. The experimental findings were corroborated by theoretical calculations. In the rhodium-catalyzed enantioselective hydrogenation of methyl 2-acetamidoacrylate (MAA), an enantiomeric ratio of 75 : 25 (R/S) was obtained for the ortho-substituted ligand.     

On the trimerization of cyanoacetylene: mechanism of formation of tricyanobenzene isomers and laboratory detection of their radio spectra

In support of a deeper understanding of the chemistry of cyanoacetylene--a known constituent of planetary atmospheres and interstellar space--theoretical and experimental studies address the chemical mechanism of dimerization and trimerization, and provide high-resolution rotational spectra of two of the trimeric products, 1,2,3- and 1,2,4-tricyanobenzene. Analysis of the rotational spectra is particularly challenging because of quadrupolar coupling from three (14)N nuclei. The laboratory rotational spectra provide the basis for future searches for these polar aromatic compounds in interstellar space by radio astronomy.     

Rheological behavior of PS-melts containing surface modified PMMA-particles

The rheological properties of polystyrene (PS) compounds containing cross-linked PMMA particles are characterized by oscillatory shear experiments, while the amount of covalently grafted carboxylic-acid terminated polystyrene (CT-PS) on their surface is varied. All samples show an additional relaxation process with a long relaxation time in the frequency range where the matrix flows. The strength of this process depends strongly on the amount of particles, i.e., on the degree of filling and, to the same extent, on the different “coverage” of the particles surface, i.e., the degree of grafting. For the highest degrees of filling and in dependence on the degree of grafting a particle network is formed which is characterized by an evolving equilibrium modulus. Moreover, compatibilization by grafting CT-PS onto the PMMA particles' surface reduces the strength of the additional relaxation process remarkably. This surprising effect is related qualitatively to the balance of the interaction between particles and the interaction between the particles and the matrix due to PS grafts. Some of these results can be understood quantitatively on the basis of the sticky hard-sphere model. Received: 3 January 2000 Accepted: 14 August 2000