Evidence for the formation of the (Ph3P)2Pt complex of 3,7-dimethyltricyclo[3.3.0.03,7]oct-1(5)-ene, the most highly pyramidalized alkene in a homologous series. Isolation and X-ray structure of the product of the ethanol addition to the complex

[reaction: see text] Attempts to isolate the (Ph(3)P)(2)Pt complex of the highly pyramidalized olefin 3,7-dimethyltricyclo[3.3.0.0(3,7)]oct-1(5)-ene 2 by generation of 2 in the presence of (Ph(3)P)(2)PtC(2)H(4), followed by crystallization of the complex (2-Pt) from THF-ethanol, resulted in the isolation of the adduct of 2-Pt with ethanol (5). Calculations confirm that addition of alcohol across the C1-C5 bond is more favorable in 2-Pt than in the corresponding (Ph(3)P)(2)Pt complexes of less pyramidalized olefins, despite the stronger Pt-C bonds in 2-Pt.     

Coupling of sequential injection analysis and capillary electrophoresis - Laser-induced fluorescence via a valve interface for on-line derivatization and analysis of amino acids and peptides

The on-line coupling of sequential injection analysis (SIA) and capillary electrophoresis (CE) via an in-line injection valve is presented. The SIA system is used for automated derivatization of amino acids and peptides. Dichlorotriazinylaminofluorescein serves as the derivatization agent, thus enabling sensitive laser-induced fluorescence detection of the derivatized analytes. The SIA procedure includes the following steps: (a) introduction of reagent and sample zones in a holding coil, (b) sample and reagent mixing in a reaction coil, (c) stop-flow step for increase of the reaction time, and (d) delivery of derivatized sample into the loop of the micro-valve interface. A small portion of the analyte zone is introduced electrokinetically in the separation capillary via the valve interface and CE analysis is performed. Factors affecting the CE separation, such as pH, the borate and sodium dodecyl sulphate concentration of the background electrolyte have been optimized. The derivatization conditions have been studied to obtain a high reaction yield in a relative short time. The transfer of a part of the reaction plug into the loop of the valve interface has been optimized. Using des-Tyr(1)-[Met]-enkephalinamide as test compound, it is demonstrated that after automated derivatization, on-line electrophoretic analysis could be achieved. Glycine has been selected as the internal standard in order to correct for variations in reaction time and filling of the injection loop. For the enkephalin, good reproducibility (RSD<4.5% calculated by the ratio of the peak areas) and linearity (0.5-5 microg mL(-1), R(2)>or=0.994) are obtained with a detection limit of 30 ng mL(-1) (S/N=3).     

Analysis of electrochemical degradation products of sulphonated azo dyes using high-performance liquid chromatography/tandem mass spectrometry

Electrochemical treatment of wastewaters containing azo dyes in the textile industry is a promising approach for their degradation. The monitoring of the course of the decomposition of azo dyes in wastewaters is essential due to the environmental impact of their degradation products. In this work, aqueous solutions of a simple azo dye with a low molecular weight (C.I. Acid Yellow 9) and more complex commercial dye (C.I. Reactive Black 5) were electrochemically treated in a laboratory-scale electrolytic cell in sodium chloride or ammonium acetate as supporting electrolytes. Ion-pairing reversed-phase high-performance liquid chromatography coupled with negative-ion electrospray ionization mass spectrometry is applied for the identification of electrochemical degradation products. In addition to simple inorganic salts, the formation of aromatic degradation products obtained due to the cleavage of azo bonds and further degradation reactions is shown, as well as chlorination where sodium chloride is the supporting electrolyte. Degradation mechanisms are suggested for the treatment with sodium chloride as the supporting electrolyte.     

A short synthesis of (+) and (−)-falcarinol

A short, practical synthesis of the bis-acetylenic natural product falcarinol 1 is reported. This method relies on the alternate functionalisation of bis-trimethylsilylbutadiyne 10. This may be achieved in one-pot, however, better yields were obtained more conventionally. Lipase mediated enzymatic kinetic resolution of the racemic adduct in an organic solvent afforded (+)-1 in 97% enantiomeric excess. The analogous process performed with racemic 3-acetoxy falcarinol 11 under aqueous conditions gave (−)-1. Oxidation of 1 with Dess-Martin periodinane gave falcarinone 2.