Mecanismes de Fragmentation de l'Oxazole

The fragmentation mechanisms of oxazole have been studied in detail on using various experimental techniques (refocusing of metastable ions, deuteration, AP measurements) and by theoretical calculations.     

A Photochemical Approach to a Potential Precursor of the Bicyclo [6.4.0] Dodecane Ring System of Taxane Diterpenes

The intermolecular [2+2] photocycloaddition of dimedone 6 and 1-acetoxy-2-methyl-5-dioxolan-1-hexene 7 followed by alkaline treatment, gave the 1,5,5,11-tetramethyl-7-dioxolan bicyclo [4,3,2]-4-decen-2,3-dione 12, and the 1,5,5-trimethyl-3-hydroxy-7-dioxolan bicyclo [5,4,1] dodecan-2,11-dione 13.     

Determination of sulfur and selected trace elements in metallothionein-like proteins using capillary electrophoresis hyphenated to inductively coupled plasma mass spectrometry with an octopole reaction cell

The determination of sulfur in biologically relevant samples such as metalloproteins is described. The analytical methodology used is based on robust on-line coupling between capillary electrophoresis (CE) and octopole reaction cell inductively-coupled plasma mass spectrometry (ORC–ICP–MS). Polyatomic ions that form in the plasma and interfere with the determination of S at mass 32 are minimised by addition of xenon to the collision cell. The method has been applied to the separation and simultaneous element-specific detection of sulfur, cadmium, copper, and zinc in commercially available metallothionein preparations (MT) and metallothionein-like proteins (MLP) extracted from liver samples of bream (Abramis brama L.) caught in the river Elbe, Germany. Instrumental detection limits have been calculated according to the German standard procedure DIN 32645 for the determination of sulfur and some simultaneously measured trace elements in aqueous solution. For sulfur detection limits down to 1.3 g L^–1 (³⁴S) and 3.2 g L^–1 (³²S) were derived. For the other trace elements determined simultaneously detection limits ranging from 300 ng L^–1 (⁵⁸Ni) to 500 ng L^–1 (⁶⁶Zn, ⁵⁵Mn) were achieved. For quantification of sulfur and cadmium in a commercially available MT preparation under hyphenated conditions the use of external calibration is suggested. Finally, the need for proper sample-preparation technique will be discussed.     

Characterization and quantification of metallothionein isoforms by capillary electrophoresis–inductively coupled plasma–isotope-dilution mass spectrometry

In a new approach to the characterization and quantification of metallothionein isoforms an on-line isotope-dilution method in combination with the coupling of capillary electrophoresis (CE) to an inductively coupled plasma-sector field mass spectrometer (ICP-SFMS) is reported. Metallothionein (MT) isoforms are separated by CE and the elements Cu, Zn, Cd, and S are detected simultaneously by use of ICP-SFMS in the medium resolution mode. On-line isotope dilution is performed by continuous introduction of an isotopically enriched, species-unspecific spike solution after the separation step. MT from rabbit liver and a further purified MT-1 isoform were quantified by determination of sulfur, and the stoichiometric compositions of the metalloprotein complexes are characterized by determination of their sulfur-to-metal ratios.     

Phase behaviour of <Emphasis Type="Italic">n</Emphasis>-hexane/perfluoro-<Emphasis Type="Italic">n</Emphasis>-hexane binary thin wetting films

We present X-ray reflectivity investigations of the concentration distribution in binary liquid thin films on silicon substrates. The liquid-vapor coexistence of the binary mixture investigated, hexane and perfluorohexane, is far from criticality. Therefore, a sharp interface separates the liquid film from the vapor. The data reveal a separation of the film in layers parallel to the substrate. A phase diagram is constructed as a projection to the (composition difference, temperature) space, covering a temperature range corresponding to the one-phase and the two-phase regime of the bulk liquid. Although the composition data indicate a mixing gap similar to that of the bulk system, there are two major differences: i) only the near-surface phase changes its composition significantly, and ii) a composition gradient in the film exists also at higher temperatures where in the bulk system the one-phase regime exists.Received: 28 April 2004, Published online: 21 September 2004PACS: 61.10.Kw X-ray reflectometry (surfaces, interfaces, films) - 64.75. + g Solubility, segregation, and mixing; phase separation - 68.15. + e Liquid thin films     

Differenzspektroskopische und pulspolarographische untersuchungen zur zusammensetzung der kupfer-alizarin s-komplexe

From differential spectrophotometric, conductometric and pulse polarographic data, three copper-Alizarin S complexes (with compositions 1:2, 1:1 and 2:1) can be identified. The copper-rich 2:1-compound can be precipitated from aqueous solution. In dimethylformamide/water solutions the copper in the 1:1-complex is bound in the peri-position.