Trace analysis of germanium

Summary The dp-polarographic and stripping voltammetric behaviour of germanium(IV) in the presence of various supporting electrolytes is discussed. Moreover, a highly sensitive adsorptive stripping voltammetric technique has been developed. The determination is based on the accumulation of germanium(IV)-diol complexes by adsorption at a hanging mercury drop electrode, followed by cathodic stripping voltammetry. Suitable for the complex forming reaction are catechol (1,2-dihydroxybenzol) and pyrogallol (1,2,3-trihydroxybenzol). By using pyrogallol the detection limit is 0.1 ng ml^–1 with a standard deviation of ±13%. A multistage combined procedure with adsorptive stripping voltammetry is described for the determination of germanium traces in ginseng and garlic. The results are compared with those using extraction-spectrophotometry and atomic absorption spectrometry.Dedicated to Prof. Dr. G. Schulze on the occasion of his 60th birthday     

Adsorptive stripping voltammetric determination of vanadium as chloranilic acid complex

Traces of vanadium(V) can be determined up to 21 ng/l by adsorptive stripping voltammetry using 2,5-dichloro-1,4-dihydroxy-3,6-benzoquinone (chloranilic acid) as complex forming reagent. The complex is stable in a 0.1 mol/l acetate buffer (pH 4.6) solution and adsorbed at the electrode surface in a potential range between –150 mV and –400 mV. The adsorption process is solved by alternating current (ac) voltammetric measurements. The method is applied to different real samples.     

Sensitive and selective determination of metabolically formed trans-dihydrodiols and phenols of benzo[a]pyrene in water and urine samples by HPLC with amperometric detection

A method has been developed to separate hydroxylated metabolites of the carcinogenic polycyclic aromatic hydrocarbon benzo[a]pyrene, i. e. trans-4,5-, 7,8-, 9,10-dihydrodiol and 1-, 3-, 7-, and 9-phenol, by HPLC with amperometric detection employing an isocratic methanol/water eluent (70:30, v/v) containing 0.5 g/L sulfuric acid and 1 g/L lithium perchlorate. Compared with the usually applied fluorescence (λ_ex = 265 nm, λ_em = 460 nm) and ultraviolet (λ = 265 nm) detection, the amperometric technique is about 2–12 times more sensitive for the determination of all metabolites investigated. The method was applied to the determination of the seven metabolites of benzo[a]pyrene in different water samples and in urine after solid-phase extraction (SPE). The results obtained by HPLC with amperometric detection after SPE enrichment from an aqueous extract of a soil sample and from the urine of a rat intragastrically treated with benzo[a]pyrene agreed well with the values determined with fluorescence and/or UV detection.     

Sensitive and selective determination of metabolically formed trans-dihydrodiols and phenols of benzo[a]pyrene in water and urine samples by HPLC with amperometric detection

A method has been developed to separate hydroxylated metabolites of the carcinogenic polycyclic aromatic hydrocarbon benzo[a]pyrene, i. e. trans-4,5-, 7,8-, 9,10-dihydrodiol and 1-, 3-, 7-, and 9-phenol, by HPLC with amperometric detection employing an isocratic methanol/water eluent (70:30, v/v) containing 0.5 g/L sulfuric acid and 1 g/L lithium perchlorate. Compared with the usually applied fluorescence (λ_ex = 265 nm, λ_em = 460 nm) and ultraviolet (λ = 265 nm) detection, the amperometric technique is about 2–12 times more sensitive for the determination of all metabolites investigated. The method was applied to the determination of the seven metabolites of benzo[a]pyrene in different water samples and in urine after solid-phase extraction (SPE). The results obtained by HPLC with amperometric detection after SPE enrichment from an aqueous extract of a soil sample and from the urine of a rat intragastrically treated with benzo[a]pyrene agreed well with the values determined with fluorescence and/or UV detection. Received: 20 December 1996 / Revised: 10 March 1997 / Accepted: 30 April 1997     

Rechnergestützte Auswertung experimenteller Inkohlungsuntersuchungen

Model investigations, carried out as laboratory coalification reactions with humous and sapropelitic sediments of different maturation degree, showed that conclusions can be drawn about the character of the parent rock of a natural gas using data of the chemical and isotopic composition of the organic substance in sediments and its coalification products.

Several examples demonstrate, that the following parameters have proved as suitable fades- and in part as maturity criteria: CH₄/Σ HKW; C₂H₆/CH₄, i-/n-C₄H₁₀, ¹³C-abundance of organic substance, ¹³C-abundance of methane.

For a complex interpretation all results obtained from coalification experiments over some years were stored in a data file. By means of cluster analysis all samples were classified in groups corresponding to their characteristics represented by the above mentioned five criteria. Four clusters resulted depending on maceral composition of the tested organic sediments. The differentiating criteria of these clusters are discussed.     

Notes on lattice points of zonotopes and lattice-face polytopes

Minkowski’s second theorem on successive minima gives an upper bound on the volume of a convex body in terms of its successive minima. We study the problem to generalize Minkowski’s bound by replacing the volume by the lattice point enumerator of a convex body. In this context we are interested in bounds on the coefficients of Ehrhart polynomials of lattice polytopes via the successive minima. Our results for lattice zonotopes and lattice-face polytopes imply, in particular, that for 0-symmetric lattice-face polytopes and lattice parallelepipeds the volume can be replaced by the lattice point enumerator.     

Chiral amphiphilic self-assembled alpha,alpha'-linked quinque-, sexi-, and septithiophenes: synthesis, stability and odd-even effects

The synthesis, characterization, and self-assembly in butanol of a series of well-defined alpha,alpha'-linked quinqui-, sexi-, and septithiophenes substituted, via ester links at their termini, by chiral oligo(ethylene oxide) chains carrying an alpha, beta, delta, and epsilon methyl, respectively, are reported. Studies of the self-assembly of these molecules using UV/visible absorption, luminescence, and circular dichroism spectroscopies reveal, for the sexithiophene case, that the magnitude of the observed Cotton effect in the aggregates diminishes progressively as the chiral substituent is moved away from the thiophene segment. The stability of the assemblies increases with the length of the oligothiophene and as the substituent chiral unit is moved away from the aromatic core, being greatest for the unsubstituted case. The sign of the Cotton effect alternates in an "odd/even" manner as the position of the chiral substituent is moved along the oligo(ethylene oxide) chain and on going from the quinquethiophene to the septithiophene having the same side chain. Atomic force microscopy on materials deposited from solution on an aluminum or glass surface and optical measurements show that capsules are formed from the oligothiophenes with H-type packing of the aromatic segments.     

Testing for affine equivalence of elliptically symmetric distributions

Let X and Y be d-dimensional random vectors having elliptically symmetric distributions. Call X and Y affinely equivalent if Y has the same distribution as AX+b for some nonsingular d×d-matrix A and some . This paper studies a class of affine invariant tests for affine equivalence under certain moment restrictions. The test statistics are measures of discrepancy between the empirical distributions of the norm of suitably standardized data.