Determination of vanadium in biological matrices by flame atomic absorption spectrometry with activated carbon enrichment

For the determination of vanadium in biological materials by flame AAS an enrichment is described which comprises chelation with oxine and adsorption on activated carbon: The relative standard deviation for 10 g V/L was found to be 6% (n=15).Dedicated to Professor Dr. Dieter Klockow on the occasion of his 60th birthday     

Effect of p-tert-Butylcalix[4]arene Fitted with Phosphinoyl Pendant Arms as Synergistic Agent in the Solvent Extraction and Separation of Some Trivalent Lanthanoids with 4-Benzoyl-3-methyl-1-phenyl-5-pyrazolone

The synergistic solvent extraction of five selected lanthanoid ions (La³⁺, Nd³⁺, Eu³⁺, Ho³⁺ and Lu³⁺) with a 4-benzoyl-3-methyl-1-phenyl-5-pyrazolone(HP) and the 5,11,17,23-tert-butyl-25,26,27,28-tetrakis(dimethylphosphinoylmethoxy)calix[4]arene, (S) in CHCl₃ has been studied. It was found that in presence of this phosphorus-containing calix[4]arene the lanthanoids have been extracted as LnP₃ · S. On the basis of the experimental data, the values of the equilibrium constants have been calculated. The influence of the synergistic agent on the extraction process has been discussed. A synergistic effect of almost three orders of magnitude occurs in the extraction of Ln(III) with mixture of HP and S. The values of the separation factors (S.F.) between the adjacent elements have been evaluated. On the basis of the IR and NMR spectra the stoichiometry and the structure of the solid complexes of Eu(III) with HP and Eu(III) with HP and S were proposed.     

Plant tissue-based amperometric electrode for eliminating ascorbic acid interferences

An application of tissue-based electrodes aimed at eliminating interferences from co-existing electroactive constituents is described. The concept is illustrated using a zucchini-containing carbon paste electrode. The presence of the enzyme ascorbic acid oxidase (AAO) in the zucchini tissue effectively eliminates contributions from ascorbic acid, thus allowing selective measurement of dopamine or norepinephrine. In comparison with analogous enzyme-based AAO electrodes, the tissue “eliminator” electrode offers high biocatalytic stability and activity and extremely low cost. The effects of various experimental variables are studied using pulse voltammetry, chronoamperometry and flow-injection amperometry. The electrode has a useful lifetime of 4 weeks. Simultaneous elimination of uric acid interferences is obtained via the co-immobilization of uricase. Oxygen background currents are eliminated in the presence of ascorbic acid.     

Enthalpic relaxation of convective desiccated trehalose-water glasses

Minimizing molecular mobility for desiccation preservation of biologics close to ambient temperature using trehalose glasses require quantitative characterization of their enthalpic relaxation at various end water contents. Differential scanning calorimetry (DSC) was used to characterize three different water contents: 0%, 1.5% and 10% over a wide range of aging temperatures. Results showed the characteristic time (τ) varies both with the water content and the aging temperature. τ increased with lowered aging temperature but showed a non-monotonous relationship as a function of water content. Fragility of trehalose glasses was analyzed using thermophysical parameters obtained from relaxation studies. The study showed trehalose to be a fragile glass former at all water contents, with 0% water samples showing a relatively stronger glass. A compromise between molecular mobility and glass fragility led to an optimal water content close to 1.5% and an aging temperature close to room temperature. This would ensure a τ value of 9000 h, which corresponds to a storage period of a year.     

Determination of in vitro antioxidant and radical scavenging activities of propofol

Propofol (2,6-diisopropylphenol) is a hypnotic intravenous agent with in vivo antioxidant properties. This study was undertaken to examine the in vitro antioxidant activity of propofol using different antioxidant tests including by 1,1-diphenyl-2-picryl-hydrazil (DPPH.) radical scavenging, metal chelating, hydrogen peroxide scavenging, superoxide anion radical scavenging, reducing power and total antioxidant activities. At the concentrations of 25, 50, and 75 microg/ml, propofol exhibited 97.7, 98.6 and 100% inhibition on peroxidation of linoleic acid emulsion, respectively. On the other hand, at the 75 microg/ml concentration of standard antioxidants such as butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT) and alpha-tocopherol exhibited 88.7, 94.5, and 70.4% inhibition on peroxidation of linoleic acid emulsion, respectively. In addition, at same concentrations, propofol was shown that it had effective reducing power, DPPH. free radical scavenging, superoxide anion radical scavenging, hydrogen peroxide scavenging and metal chelating activities. These various antioxidant activities were compared to standard antioxidants such as BHA, BHT and alpha-tocopherol. These results indicate that propofol prevents lipid peroxidation and radicalic chain reactions. At the same time, propofol revealed more effective antioxidant capacity than BHA, BHT and alpha-tocopherol.     

A novel (E,E)-dioxime and its mono-, di- and trinuclear complexes bearing tetradentate octyl sulfanyl phenylamino substituents. Synthesis,characterization and electrochemical properties of its transition metal complexes

A new vic-dioxime, 13,14-bis-(hydroxyimino)-9,12,15,18-diazadithiaoctacosane, has been synthesized from 2-octylsulfanylaminobenzene and (E,E)-dichloroglyoxime. Mononuclear transition metal complexes of Ni^II, Cu^II, Co^II and Fe^II have been prepared and were found to have a metal–ligand ratio of 1:2. The synthesis of di- and trinuclear complexes was achieved with U^IVO₂ and Cu^II depending on the stoichiometry of the reactants. The complexes were characterized by elemental analysis, ¹H-n.m.r., u.v.–vis, i.r., f.a.b.-m.s. and by cyclic voltammetry.     

Reaktionen cyclischer Oxalylverbindungen, 34. Mitt.: Synthese von Dibenzoylacet-N-carboxyalkylamiden und semiempirische Rechnungen zur Keto-Enol Tautomerie

Summary 4-Benzoyl-5-phenylfuran-2,3-dione (1) and the urethanes2 combine under loss of carbon monoxide yielding the open chain dibenzoylacetic acid derivatives3 and4. 3a, b only can be cyclized to the oxazinone5. The keto-enole tautomerism3 4 is further investigated with aid of semiempirical quantum chemical calculations, based upon the molecular geometry of3a, deduced from an X-ray study.

Frau Univ. Prof. Dr. Helga Wittmann mit den besten Wünschen zum 70. Geburtstag gewidmet.     

Modification of Escherichia coli single-stranded DNA binding protein with gold nanoparticles for electrochemical detection of DNA hybridization

The unique binding event between Escherichia coli single-stranded DNA binding protein (SSB) and single-stranded oligonucleotides conjugated to gold (Au) nanoparticles is utilized for the electrochemical detection of DNA hybridization. SSB was attached onto a self-assembled monolayer (SAM) of single-stranded oligonucleotide modified Au nanoparticle, and the resulting Au-tagged SSB was used as the hybridization label. Changes in the Au oxidation signal was monitored upon binding of Au tagged SSB to probe and hybrid on the electrode surface. The amplified oxidation signal of Au nanoparticles provided a detection limit of 2.17 pM target DNA, which can be applied to genetic diagnosis applications. This work presented here has important implications with regard to combining a biological binding event between a protein and DNA with a solid transducer and metal nanoparticles.     

Efficient syntheses of (±)-hydrangenol, (±)-phyllodulcin and (±)-macrophyllol

In this paper we report on a efficient and flexible synthetic route towards the total syntheses of the dihydrocoumarine derivatives hydrangenol (1), phyllodulcin (1a) and macrophyllol (6b). The syntheses started with a readily available phosphonium salt 2 and suitable modified benzaldehydes 3/3a/3b resulting in 46 to 61% overall yields in three to four-steps sequences. The racemic products could be separated by chiral HPLC. The evidence of the (R)-enantiomer for sweetness could be demonstrated for 1a.     

Manganese(III) acetate mediated synthesis of 3-trifluoroacetyl-4,5-dihydrofurans and 3-(dihydrofuran-2(3H)-ylidene)-1,1,1-trifluoroacetones by free radical cyclization. Part 1

2-Trifluoroacetyl-4,5-dihydrofurans were obtained by manganese(III) acetate mediated radical cyclization of trifluoromethyl-1,3-dicarbonyl compounds (1a-c) with conjugated alkenes (2a-h). The reaction of 1,1,1-trifluoropentane-2,4-dione (1a) with propenylbenzene and 1,1-diphenyl-1-butene surprisingly yielded 3-(dihydrofuran-2(3H)-ylidene)-1,1,1-trifluoroacetones besides 3-trifluoroacetyl-4,5-dihydrofurans.