Anab initio investigation of Cu2Se and Cu4Se2

Summary Experimentally known copper selenium clusters show extraordinary geometrical features, especially short Cu-Cu distances. We report the first theoretical investigation of Cu₂Se and Cu₄Se₂. Various quantum chemical methods (SCF, MP2, CPF, CCSD, CCSD(T), LDF) are applied to determine the importance of dynamic electron correlation. We find that inclusion of correlation does not essentially change the electronic structure of the clusters but has a strong influence on geometries. To reduce the computational effort we apply effective core potentials (ECPs) in combination with small, but carefully optimized basis sets. The applicability of simple modellings of correlation energies for approximate inclusion of correlation effects in SCF geometry optimizations is tested.     

One-step cleanup for PAH residue analysis in plant matrices using size-exclusion chromatography

A new one-step cleanup procedure, based on size-exclusion chromatography (SEC), usable for the extracts from accelerated solvent extraction (ASE), Soxhlet extraction, or ultrasonic extraction (USE), is described. The method is suitable for the determination of polycyclic aromatic hydrocarbons (PAHs), especially from very complicated plant matrices (e.g. pine needles, deciduous leaves, mosses). The main improvement compared with previous conventional procedures is that analyte peaks barely overlap with matrix peaks in the chromatograms and that it is a very rapid and simple one-step procedure with clearly improved analytical performance. Essential advantages of this SEC procedure are the sharper GC-MS chromatograms for the PAH fraction at retention times between 9.2 and 12.0 min, distinctly separated substance peaks resulting in better analysis, shorter running times, and lower solvent consumption.     

Separation of enzymes from Candida boidinii crude extract by continuous flow zone electrophoresis.

Separation of the enzymes formate dehydrogenase, formaldehyde dehydrogenase and methanol oxidase from Candida boidinii crude extract has been explored using continuous flow zone electrophoresis in the VaP-22 and the scaled-up VaP-220 electrophoresis apparatus. Yields up to 95% and purification factors between 3 and 7 were obtained, together with separation of cell debris from the enzymes. Multiple injections of sample were used to obtain a protein throughput of 46.2 mg/h in the VaP-22. A tenfold higher throughput was achieved using the VaP-220. Correlation of the electrophoretic mobility in continuous flow zone electrophoresis with the elution behavior in ion-exchange chromatography confirmed the primary role of net surface charge in the separation of biological molecules. Proteins and enzymes with differences greater than 0.05 M elution molarities in ion-exchange chromatography can be separated. This corresponds to a preparative scale (mg/h or g/h) separation of proteins and enzymes whose difference in apparent electrophoretic mobility is greater than 0.70 x 10(-5) cm2/(V.s).     

ACIDITY DEPENDENCE OF THE ABSORPTION AND FLUORESCENCE SPECTRA OF ISOFLAVONE AND 7-HYDROXYISOFLAVONE

-The pH and H₀ dependence of the absorption and fluorescence spectra of isoflavone and 7-hydroxyisoflavone are reported. Isoflavone is fluorescent in acidic solution only, whereas 7-hydroxyisoflavone is fluorescent in all acidity ranges under investigation. Ground and first excited singlet state p K _a's have been determined spectrophotometrically and fluorimetrically, respectively. Excited state protolytic equilibration processes via a second order reaction (proton gain) are found to be too slow to compete efficiently with fluorescence. This is deduced from the close agreement between the p K _a's of the conjugate acids obtained by absorption and fluorescence titrations. On the other hand, photodissociation of 7-hydroxyisoflavone proceeds faster than its fluorescence decays. The experimental p K _a(S₁) is in fair agreement with the calculated one. 7-Hydroxyisofiavone forms a phototautomer (or exciplex) in the pH 2 to H₀-1 acidity range, which is characterized by its long wavelength emission. Quantum efficiencies are given for isoflavone and 7-hydroxyisoflavone in aqueous solutions of various acidities. Deuteration effects thereon are discussed.     

Der Verlauf der Umlagerung von Phenacylsulfenylmorpholid zu Phenylglyoxylsäurethionmorpholid in Gegenwart von Schwefel

Zusammenfassung Bei der Einwirkung von elementarem Schwefel auf Phenacyl-sulfenylmorpholid entsteht unter H₂S-Abspaltung Phenylglyoxyl-säurethionmorpholid. Durch Einsatz von radioaktivem Schwefel wurde festgestellt, daß diese Umlagerungsreaktion über die Stufe einergem. Dimercaptoverbindung verläuft.

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Reaction of elementary sulfur with phenacylsulfenylmorpholide gives phenylglyoxylic acid thionmorpholide while hydrogen sulfide is eliminated. The rearrangement proceeds, as was shown by use of radioactive sulfur, via agem. dimercaptocompound as intermediate.

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47. Mitt.:F. Asinger, W. Schäfer undA. Saus, Mh. Chem.96, 1265 (1965).

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Teil der DissertationA. Saus, Techn. Hochsch. Aachen, 1964.     

Über die Aufnahme von Metall-Nitrilotriessigsäure-Komplexen durch Anionenaustauscher

Zusammenfassung Die Aufnahme von Nitrilotriessigsäure-Komplexen von Strontium, Blei, Yttrium, Wismut und Thorium durch den Anionenaustauscher Dowex-1 wurde untersucht, indem die Elutionsgeschwindigkeiten radioaktiver Isotope dieser Elemente aus Austauschersäulen gemessen wurden. Für die Versuche wurde mit Nitrilotriacetat (NTA) beladener Austauscher verwendet; als Elutionsmittel dienten NTA-Lösungen verschiedener Konzentration. Die ermittelten Verteilungskoeffizienten (Austauscher/Lösung) geben Hinweise auf die Ladungszahlen der für die Aufnahme in den Austauscher maßgeblichen Metall-NTA-Komplexe und damit auf deren Zusammensetzung. Sie liefern auch Aussagen über die Wechselwirkung zwischen den komplexen Anionen und dem Austauscher. Anwendungsmöglichkeiten der Aufnahme von NTA-Komplexen in den Anionenaustauscher für radiochemische Trennungen werden aufgezeigt.Mit 3 Abbildungen     

Zur Bildung von Xylol-tricarbonylchrom (Dimethylbenchrotrenen) aus Di-n-butylether und Hexacarbonylchrom

The reaction of fluorenone ethyleneketal (9), diphenic anhydride as well as of biphenyls such as4 with Cr(CO)₆ in refluxing di-n-butylether (BE) gives dimethylbenchrotrenes [xylene-Cr(CO)₃,7] which are also formed by refluxing pureBE with Cr(CO)₆—although with much lower yields. Similarily, from di-n-pentylether and Cr(CO)₆ isobutyl- and 1-methyl-3-propyl-benchrotrene (13 and14) were obtained, whilst from di-n-propyl- and-hexylether, resp., and Cr(CO)₆ no benchrotrenes could be isolated.Tentative assumptions on the catalytic action of certain functional groups were confirmed by the reaction ofBE and Cr(CO)₆ in the presence of carbonamides, such as acetamide, urea and pyrrolidone, where 1,4-dimethylbenchrotrene (7 c) was formed with appreciable yields.Studies using dideuteratedBE showed that—at least for the reaction of9 with Cr(CO)₆ (giving a much lower yield of7 than with undeuteratedBE)—a simple bimolecular mechanism can be excluded.

     

Application of high-performance liquid chromatography of some antibiotics in clinical microbiology

During recent years high-performance liquid chromatography has become an excellent tool for the determination of antibiotics in biological fluids. Compared with biological assays, the major benefits of this method are specificity and rapidity. In particular, the determination of biologically inactive metabolites emphasizes that this technique plays an outstanding role for the analysis of antibiotics. This paper describes how the method can be used in the analysis of several antibiotics and demonstrates the efficacy of this method for clinical microbiology. Methods for the determination in biological fluids of acylaminopenicillins (azlocillin, mezlocillin, piperacillin and aspoxicillin), quinolones (ciprofloxacine, norfloxacine and ofloxacine), a penem (imipenem) and a cephalosporin (cefixime) are summarized. Furthermore, their application to in vitro studies and their trial in clinical studies are described.