A solvent-free synthesis of coumarins using a Wells-Dawson heteropolyacid as catalyst

Substituted coumarins are synthesized from phenols and β-ketoesters by the Pechmann reaction, using a Wells-Dawson heteropolyacid (H₆P₂W₁₈O₆₂·24H₂O) as catalyst by a solvent-free procedure. This one requires low reaction times, 130 °C temperature and as little as 1 mol % of Wells-Dawson acid, obtaining good to excellent yields of coumarins. The catalyst showed to be reusable with no differences in the yields. The results are compared with those of the reactions performed in toluene solution. The presented synthetic procedure is a convenient, clean and fast alternative for synthesizing 4-substituted coumarins (17 examples).     

Design of an experimental procedure for energy evaluation from biomass

The rational and sustainable exploitation of nature resources is one of the priority objectives of our society. In this article a method is proposed to evaluate and exploit the energetic resources contained in different forest formations. This method is based on the use of a combustion bomb calorimeter to determine the calorific values of the different samples studied. These results were complemented with chemical analysis of the samples and with environmental and geomorphological studies of the zones were samples were taken. The results obtained during the last 3 years for the residual biomass originated from the forest formations existing in Galicia ensure the reliability and usefulness of the method that can be extended to any forest formation all over the world.     

Unavoidable Traces Of Set Systems

Sauer, Shelah, Vapnik and Chervonenkis proved that if a set system on n vertices contains many sets, then the set system has full trace on a large set. Although the restriction on the size of the groundset cannot be lifted, Frankl and Pach found a trace structure that is guaranteed to occur in uniform set systems even if we do not bound the size of the groundset. In this note we shall give three sequences of structures such that every set system consisting of sufficiently many sets contains at least one of these structures with many sets.     

Higher Order Peak Algebras

Using the theory of noncommutative symmetric functions, we introduce the higher order peak algebras (Sym(N))_N≥1, a sequence of graded Hopf algebras which contain the descent algebra and the usual peak algebra as initial cases (N=1 and N=2). We compute their Hilbert series, introduce and study several combinatorial bases, and establish various algebraic identities related to the multisection of formal power series with noncommutative coefficients. Received November 19, 2004     

Determination of melengestrol acetate in bovine tissues by automated coupled-column normal-phase high-performance liquid chromatography

A method has been developed for the determination of melengestrol acetate in bovine tissues at lower levels than previously reported. Liquid-liquid extraction of tissue homogenates provided crude clean-up while final isolation, screening, and quantification was done on-line with an automated, normal-phase, coupled-column high-performance liquid chromatographic system. The chromatographic system included phenyl and silica analytical columns for the purposes of isolation and final separation, respectively. These columns provided a large difference in selectivity when operated under normal-phase conditions which allowed for the efficient isolation of melengestrol acetate from the complex tissue extracts. Mobile phases were composed of hexane and dichloromethane modified with methanol and water. Transfer and enrichment of the analyte from the primary phenyl column to the silica column was via a short (12 mm x 4 mm I.D.) silica column. Regeneration and equilibration of the phenyl column was performed after the injection of each tissue extract and was accomplished simultaneously while analytical separation occurred on the final silica column. Routing of the mobile phases and regeneration solvent was performed with automated switching valves. The total time required for each analysis was 12 min. Quantification is demonstrated using external standards with UV detection at 287 nm. The overall recovery of the method was 86% with a coefficient of variation of 9.84% at the 10 ppb [the American billion (10(9] is used in this article] level in bovine liver extracts.     

Measurement of elastin hydrolysis by reverse-phase HPLC with on-line post-colum derivatization

Summary Excessive breakdown of elastin, a structural protein, may be related to aortic disease and emphysema. Since L-valyl-L-proline occurs in high concentrations in elastin, a rapid and sensitive method using HPLC with post-column on-line derivatization was used to measure the dipeptide from swine aortic tissue, and the amount of elastin present was determined. Elastin was extracted by alkaline hydrolysis. After neutralization and filtration, the sample was injected onto a ODS-2 gel column, and the dipeptide was eluted by a linear gradient of 0 to 10% of 1-propanol in 50 mM heptafluorobutyrate, pH 3, at a flow rate of 1 ml/min. The eluent was reacted with fluorescamine at pH 8.6, and fluorescence was detected at an excitation wavelength of 395 nm and a 455 nm cutoff emission filter.Presented at the 17th International Symposium on Chromatography, September 25–30, 1988, Vienna, Austria.     

Preparation of rhodium–phyllosilicate catalysts without leaching in liquid-phase 1-hexene hydrogenation

Rhodium catalysts have been prepared on palygorskite and montmorillonite (clay) supports by reduction with hydrogen (1 atmosphere) at room temperature of a cationic organometallic rhodium compound anchored to the support. The activity of these catalysts for the hydrogenation of liquid-phase 1-hexene remains constant with increase of prehydrogenation time and with re-use for several runs. No rhodium leaching is observed.     

Quantitative Bestimmungen mittels cyclischer Voltammetrie an der Phasengrenze zweier mischbarer Elektrolytl?sungen

Summary This paper presents some applications of cyclic voltammetry at the interface of two immiscible electrolyte solutions by means of an experimental set-up described in a former publication. When using special sample preparation good results are obtained for the determination of iodide and quinine in pharmaceutical products as well as for the determination of quinine in tonic water and dodecylsulfate in a tooth-salt.

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Herrn Prof. Dr. Günther Tölg zum 60. Geburtstag gewidmet