Application of chemometric methods in Auger electron microanalysis of composites

Principal component analysis and cluster analysis have been used in AES investigations of fibre-matrix interactions in alumina fibre reinforced MgLi-alloys prepared by high-pressure infiltration. The samples have been fractured in ultra high vacuum to expose surfaces and interfaces without contamination. All main components exhibit Auger valence band transitions which change their shape with the chemical state. Chemometric methods have been utilized to identify characteristic peak shapes and to classify the investigated areas by composition. Fibre fracture surfaces are characterized by Al, magnesia and Li oxide formed by a redox reaction of alumina with Mg and Li penetrating along grain boundaries. For samples with high silica content a thin interfacial oxide layer on matrix grain boundaries and matrix-fibre interfaces has been found.     

Simplified, rapid and inexpensive extraction procedure for a high-performance liquid chromatographic method for determination of disopyramide and its main metabolite mono-N-dealkylated disopyramide in serum.

A simplified, rapid and inexpensive extraction procedure for the determination of the antiarrhythmic drug disopyramide and its main metabolite mono-N-desalkylated disopyramide in serum by high-performance liquid chromatography has been developed. The analysis uses ultraviolet detection at 254 nm, and a 5 micron reversed-phase column with a mobile phase of water-triethylamine-acetonitrile-PIC-B8 reagent. Serum extraction is performed with dichloromethane and 1 M sodium hydroxide. p-Chlorodisopyramide is used as internal standard. Recovery rates were 94.5% (S.D. 5.7%) for disopyramide, 96.8% (S.D. 2.2%) for mono-N-desalkylated disopyramide and 97.9% (S.D. 2.8%) for the internal standard.     

Laser spectroscopic excitation function and reaction threshold studies of the H + DCl --> HCl + D gas-phase isotope exchange reaction

The dynamics of the gas-phase hydrogen atom exchange reaction H + DCl --> HCl + D were studied using the pulsed laser photolysis/laser induced fluorescence "pump-and-probe" method. Laser photolysis of H2S at 222 nm was used to generate nonequilibrium distributions of translationally excited hydrogen atoms at high dilution in a flowing moderator gas (Ar)/reagent (DCl) mixture. H and D atoms were detected with sub-Doppler resolution via Lyman-alpha laser induced fluorescence spectroscopy, which allowed the measurement of the line shapes of the moderated H atom Doppler profiles as well as the concentration of the D atoms produced in the H + DCl --> HCl + D reaction. From the measured H atom Doppler profiles, the time evolution of the initially generated nascent nonequilibrium H atom speed distribution toward its room-temperature thermal equilibrium form was determined. In this way, the excitation function and the reaction threshold (E0 = 0.65 +/- 0.13 eV) for the H + DCl --> HCl + D reaction could be determined from the measured nonequilibrium D atom formation rates and single collision absolute reaction cross-section values of 0.12 +/- 0.04 A2 and 0.45 +/- 0.11 A2 measured at reagent collision energies of 1.0 and 1.4 eV, respectively.     

Gas chromatographic profiling of phenolic acids in urine of patients with cirrhosis of the liver

Phenolic acids are analysed within the profile of the organic acids in urine of patients with cirrhosis. For the following constituents an increased urinary excretion is observed: 4-hydroxyphenylpyruvic acid, 4-hydroxyphenyllactic acid, 4-hydroxyphenylacetic acid, 4-hydroxybenzoic acid, 4-hydroxyhippuric acid, vanillic acid, homovanillic acid, 4-hydroxymandelic acid, 4-hydroxy-3-methoxyphenylpropionic acid and p-cresol. The phenols are metabolites of tyrosine and are produced in the liver, in extrahepatic tissues and by intestinal microorganisms. They are suggested as biochemical control parameters for the metabolizing function of the liver, for the effect of therapy and for the existence of portal-systemic venous collaterals.     

Syntheses of Thailandepsin B Pseudo-Natural Products: Access to New Highly Potent HDAC Inhibitors via Late-Stage Modification

New Thailandepsin B pseudo-natural products have been prepared. Our synthetic strategy offers the possibility to introduce varying warheads via late stage modification. Additionally, it gives access to the asymmetric branched allylic ester moiety of the natural product in a highly diastereoselective manner applying rhodium-catalyzed hydrooxycarbonylation. The newly developed pseudo-natural products are extremely potent and selective HDAC inhibitors. The non-proteinogenic amino acid d -norleucine was obtained enantioselectively by a recently developed method of rhodium-catalyzed hydroamination.     

Eine Einfache Synthese von N-Acyl-Glykosylaminen

Abstract

D-Ribose, D-arabinose and D-glucose react with nitriles in liquid hydrogen fluoride to give the corresponding 1,2-cis configurated N-acyl-pento (or hexo) furanosyl amines 1-7 and 9. D-Xylose gives the ct-pyranosyl isomer 8 beside the α-furanosyl main product 7. D-Mannose and L-rhamnose yield the N-acyl-α-hexopyranosyl amines 10 and 11.