INAA determination of holmium in submilligram samples of cosmochemical and geochemical interest and the second-order activation interference

Second-order neutron activation becomes a serious interference in NAA determinations of REE in submilligram samples of meteoritic and terrestrial materials when neutron fluences reach levels of 10²⁰ n·cm^–2 or more. The Dy-interference to Ho determination and the Eu-interference to Gd determination are quite, large. We discuss the importance of second-order activation interferences in REE determinations, and present an experimental method to correct the Dy-interference to Ho determination by INAA. Ho concentrations in splits of less than 0.2 mg of BCR-1 and SP can be accurately determined by INAA with a neutron fluence of 2·10²⁰ n·cm^–2 in spite of large Dy interferences of up to 200%. It is necessary for NAA determinations of REE with high neutron fluences that each REE standard be separated from its neighboring REE, in order to correct the second-order activation interferences experimentally.     

Cu(I) catalyst in DMF: an efficient catalytic system for the synthesis of furans from 2-(1-alkynyl)-2-alken-1-ones

The cyclization of 2-(1-alkynyl)-2-alken-1-ones 1 proceeded very smoothly in the presence of alcohols 2 with a catalytic amount of Cu(I)Br in DMF at 80 degrees C, leading to the formation of highly substituted furans 3. The catalytic system reported herein is easy to handle, compared to the previously known system wherein the reaction between 1 and 2 needed to use moisture sensitive gold(III) chloride.     

Synthesis and characterization of flavylium salts having three types color depending on recrystallization conditions

Three types of flavylium salts (FVs, yellow, green and red) have been synthesized and the colors depended on recrystallization conditions. The existence of these color states was confirmed by diffuse reflectance spectra. The spectra were almost the same as the absorption spectra in ethanol solution. The molecular state of FVs in crystals will be the same as that in solutions. The crystal colors of the FVs are controlled by the recrystallization conditions.     

Voltammetric investigation of avidin-biotin complex formation using an electroactive bisbiotinyl compound

Formation of avidin-biotin complex was investigated using bisbiotinyl thionine (BBT) by means of voltammetric techniques. Thionine is an electroactive compound and has two amino groups that are necessary for the reaction with a biotinylation reagent. The biotinylation of thionine produces a new reagent with two biotin moieties at each end of thionine. Three BBTs of different lengths of the spacer that connects the biotin moiety to the thionine moiety were prepared. The avidin-biotin binding assay was achieved by measuring the electrode response of the thionine moiety in BBT. The binding affinity and the conformation of complex, which depended on the length of spacer, are discussed. BBT in which the spacer is shortest (BBT-S, distance between carbonyl group of the two biotin moieties: 11 Å) binds with only one avidin molecule. BBT with medium length of spacer (BBT-M, 28.8 Å) forms the complex with two avidin molecules. BBT with the longest spacer (BBT-L, 46.6 Å) allows binding with two avidin molecules as well as intramolecular binding within one avidin molecule. The affinity constants of BBT-S, BBT-M and BBT-L for avidin were estimated to be 7.0 × 10¹² M⁻¹, 3.2 × 10¹² M⁻¹ and 4.0 × 10¹² M⁻¹, respectively.     

Purification of a marine bacterial glucose dehydrogenase fromCytophaga marinoflava and its application for measurement of 1,5-anhydro-d-glucitol

A novel glucose dehydrogenase (GDH) from a marine bacteriumCytophaga marinoflava IFO 14170 was isolated from its membrane fraction. This GDH catalyzes the oxidation of a hydroxy group of glucose, but does not react in its C-l position. This enzyme is composed of a single peptide with a mol wt of 67,000. The GDH can react under high salinity. The optimum pH is around 8.0, showing a typical property of marine bacterial enzymes. Using this novel enzyme, an enzymatic determination of 1,5-anhydro-D-glucitol (1,5AG) utilizing 2,6-dichrolophenolindophenol (DCIP) and phenazine methosulfate (PMS) as electron mediators was caried out. A good linear correlation was observed from 0.5 mM to 4 mM of 1,5AG.     

Decomposition analyses of the intermolecular interaction energies in two π?π stacking complexes: Quinhydrone and N,N,N′, N′-tetramethyl-P-diaminobenzene-chloranil complex

Although there is a similarity in the orbital interaction scheme between quinhydrone and N,N,N′,N′-tetramethyl-p-diaminobenzene-chloranil complex, the stacking conformations are different from each other. The former prefers the half-stacked conformation, whereas the latter prefers the completely stacked conformation. We have done ab initio molecular orbital calculations and decomposition analyses of the intermolecular interaction energies to clarify the origin of the different stacking conformations. It was concluded that the main origin is the difference in the steric part of the interaction energies. © 1994 by John Wiley & Sons, Inc.     

Studien Über die Saponine aus der Arznei-Ginseng-Wurzel: Massenspektren von Ginsenoside-Rg1-Decaacetat und Verwandten Verbindungen

Mass spectra of ginsenoside-Rg1 deca-acetate

1 Siehe Lit.2.

and the related dammaran-type triterpene saponin acetates have been studied and a comment is given on the structure of panaxoside A (=ginsenoside-Rg1) proposed by Elyakov, et al .     

Thermal and palladium-catalyzed [3 + 2] synthesis of cyclopentadienone acetals from cyclopropenone acetals and acetylenes

[reaction: see text] Substituted cyclopentadienone acetals (CPDAs) were synthesized by a thermal or palladium-catalyzed [3 + 2] cycloaddition reaction of a substituted cyclopropenone acetal to an electron-deficient acetylene. The synthesis afforded di-, tri-, and tetra-substituted CPDAs of considerable structural varieties that undergo Diels-Alder reaction to produce bicyclo[2.2.1]heptenes.     

Ion-exclusion chromatography with conductimetric detection of aliphatic carboxylic acids on a weakly acidic cation-exchange resin by elution with benzoic acid-beta-cyclodextrin

In this study, an aqueous solution consisting of benzoic acid with low background conductivity and beta-cyclodextrin (beta-CD) of hydrophilic nature and the inclusion effect to benzoic acid were used as eluent for the ion-exclusion chromatographic separation of aliphatic carboxylic acids with different pKa values and hydrophobicity on a polymethacrylate-based weakly acidic cation-exchange resin in the H+ form. With increasing concentration of beta-cyclodextrin in the eluent, the retention times of the carboxylic acids decreased due to the increased hydrophilicity of the polymethacrylate-based cation-exchange resin surface from the adsorption of OH groups of beta-cyclodextrin. Moreover, the eluent background conductivity decreased with increasing concentration of beta-cyclodextrin in 1 mM benzoic acid, which could result in higher sensitivity for conductimetric detection. The ion-exclusion chromatographic separation of carboxylic acids with high resolution and sensitivity was accomplished successfully by elution with a 1 mM benzoic acid-10 mM cyclodextrin solution without chemical suppression.