Flotation—spectrophotometric determination of osmium with thiocyanate and methylene blue

A sensitive flotation—spectrophotometric method, based on the ion associate formed by the anionic thiocyanate complex of osmium with the basic dye methylene blue (MB) is described. The ion associate precipitates when the aqueous solution is shaken with toluene, and the separated and washed compound is dissolved in acetone. The molar absorptivity is 2.2 × 10⁵ l mol^-1 cm^-1 at 655 nm. Beer's law is obeyed. The molar ratio of Os:SCN:MB in the separated and washed ion associate is 1:6:3. Ruthenium reacts similarly. The method is applied to the determination of traces of osmium in crucible platinum after separation of osmium by distillation as tetroxide.     

Interaction of water with the regenerated cellulose membrane studied by DSC

One to three endothermal peaks atributted to melting of bulk and interfacial water were observed by DSC in the regenerated cellulose — water system. The profiles of thermal effects depend on water content, time of conditioning, film pretreatment and the conditions applied during the preceding freezing-thawing cycles. The occurrence might be deduced of melting-crystallisation processes. A large amount of non-freezable strongly bounded water was also detected. Although cellulose absorbs water quickly after immersion, the structural changes consisting on ordering of polymer fraction occur during further conditioning due to increase in strength of water binding. Using the membranes in the separation module at 90°C causes weakening of these bonds. Differences between interaction of particular cellulose films with water can be detected during the first, the second and the third heating. This revised version was published online in July 2006 with corrections to the Cover Date.     

A vector-sum theorem in two-dimensional space

Given a finite setX of vectors from the unit ball of the max norm in the twodimensional space whose sum is zero, it is always possible to writeX = {x₁, , x_n} in such a way that the first coordinates of each partial sum lie in [–1, 1] and the second coordinates lie in [–C, C] whereC is a universal constant.     

Synthesis and stereochemical studies of 6-substituted 1H,3H,6H,7aH-3,3-dimethylimidazo-[1,5-c]thiazol-5-one-7-thiones

The reaction of (4S)-5,5-dimethyl-4-thiazolidine-carboxylic acid 1 with alkyl and aryl isothiocyanates 2 gave bicyclic thiohydantoins 3 . The (2R,4S)- and (2S,4S)-mixtures of 2-substituted 5,5-dimethyl-4-thiazolidine-carboxylic acids 4 and 8 containing two centers of chirality in the analogous reaction afforded thiohydantoins 7 and 10 , respectively, with (1R)-configuration. In some cases we managed to isolate the thioureido acid intermediates 6 and 9 or their triethylamine salts which afforded the corresponding bicycles 7 and 10 under thermal cyclization or acidification. The stereochemistry has been elucidated by high resolution ram studies, optical rotation measurements and X-ray crystallography.     

Preparation and investigation of structural and photocatalytic properties of phosphate modified titanium dioxide

A series of high surface area titanium dioxide samples (P-TiO₂) with varying phosphate content have been prepared by the sol–gel technique. The structural characterization of the samples included X-ray powder diffraction, diffuse reflectance infrared and UV–vis spectroscopy (DRIFT and UV–vis–DR), and nitrogen adsorption measurements. The structural properties of the P-TiO₂ samples significantly changed with the phosphate content and calcination temperature. According to XRD data the presence of phosphate shifts the anatase rutile phase transition to higher temperatures, revealing that phosphate improves the thermal stability of the samples. The specific surface area and the semiconductor band gap energy increase with the phosphate content.

The photocatalytic activity of TiO₂ and P-TiO₂ was studied by phenol degradation in liquid phase. A small amount of phosphate of the catalysts increases the photocatalytic activity, but further increase of the P/Ti molar ratio (above 0.01), leads to a considerable loss in activity. The optimal calcination temperature of P-TiO₂ was 300–500 °C. The phenol conversion rate is highest with catalysts calcined at 700 °C, but phenol does not degrade to carbon dioxide.     

Thioacetylacetone: structural and vibrational assignments.

Thioacetylacetone and its variously deuterated isotopomers have been investigated using electronic and vibrational spectroscopy combined with quantum chemical calculations. Thioacetylacetone is known for its photochromic properties, but the structures of the initial and final forms have been the subject of a long debate. Analysis of the IR spectra recorded in low-temperature argon and xenon matrices, room-temperature solutions, and in the gas phase has allowed us to establish the nature of the photochromic species and of its precursor. Similar to the case of another beta-thioxoketone, monothiodibenzoylmethane, the photo-product has been assigned to the nonchelated SH exo-rotamer of the (Z)-enethiol tautomeric form, whereas the dominant ground-state species corresponds to the chelated (Z)-enol tautomeric form. Detailed vibrational assignments have been proposed for both forms based on quantum chemical calculations and polarization experiments. In the case of the chelated (Z)-enol species prevailing in the ground state, a second-order perturbative anharmonic analysis at the B3LYP/cc-pVTZ level indicated strong anharmonic effects associated with the intramolecular hydrogen bond, leading to a shift of more than 600 cm-1 of the wavenumber of the OH-stretching vibration. A small fraction of the SH endo-rotameric chelated (Z)-enethiol form was also detected under unperturbed conditions. The (Z)-enethiol form can be converted into the (Z)-enol form by irradiation at 290 nm.     

Studies on the copolymerization of unsaturated 1,3-dioxane derivatives—IV. Radical copolymerization of 2-furyl-5,5-dimethyl-1,3-dioxane with maleic anhydride

The copolymerization of 2-furyl-5,5-dimethyl-1,3-dioxane with maleic anhydride in the presence of a radical catalyst yields equimolar, alternating copolymers in which the furyl units have 2,5-linkage. It has been shown that 2-furyl-5,5-dimethyl-1,3-dioxane forms a charge transfer complex with maleic anhydride. The equilibrium constant for the complex was determined by NMR spectroscopy.     

An efficient reagent for the phosphorylation of deoxyribonucleosides, DNA oligonucleotides, and their thermolytic analogues

[reaction: see text] The phosphoramidite 11 was prepared in three steps from methyl 2-mercaptoacetate and demonstrated efficiency in the synthesis of conventional 5'-/3'-phosphate/thiophosphate monoester derivatives of 2'-deoxyribonucleosides and DNA oligonucleotides. Moreover, the use of 11 has enabled the preparation of the dinucleoside phosphorothioate analogue 26 in high yields (>95%) with minimal cleavage (<2%) of the thermolytic thiophosphate protecting group.     

Determination of total carbon and total organic carbon from volatile air pollutants. Part I

Summary A new method of collection of representative air samples for the determination of TC and TOC from volatile air pollutants has been developed. The organic substances undergo combustion and only the carbon dioxide produced is concentrated on molecular sieve 5 A at ambient temperature. The CO₂ is subsequently liberated by thermal desorption at ca. 380°C in a stream of purified gas. Atmospheric CO₂ must be removed first and this can be done (at the sample flow rate of 700 ml/min) by a layer of Ascarite heated at 90° C. Organic compounds passing through the layer are then combusted by a dynamic method utilizing Körbl catalyst and the CO₂ formed is concentrated on a molecular sieve 5 A, followed by thermal desorption and final determination. Organic acids are also retained by the first CO₂ absorber. A diffusion cell for preparation of the mixtures of purified air with vapours of organic compounds is described.

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Zusammenfassung Eine neue Anreicherungsmethode zur Gewinnung representativer Luftproben zur Bestimmung des Gesamtkohlenstoffgehaltes und des Gehaltes an organischem Kohlenstoff (TOC) aus flüchtigen Luftverunreinigungen wurde entwickelt. Während der Probenahme werden die flüchtigen Verunreinigungen verbrannt und nur das entstandene Kohlendioxid bei Zimmertemperatur am Molekularsieb 5A angereichert. Anschließend wird CO₂ bei ca. 380° C im gereinigten Gasstrom thermisch desorbiert. Bei der TOC-Bestimmung muß atmosphärisches CO₂ vorangehend aus dem Luftstrom entfernt werden und wird an einer auf 90° C erwärmten Ascariteschicht gebunden. Die durchfließenden organischen Verbindungen werden dann im dynamischen System am Körblkatalysator oxydiert, das entstandene CO₂ am Molekularsieb 5A angereichert, thermisch desorbiert und einer Endbestimmung zugeführt. Organische Säuren werden gleichfalls durch den ersten CO₂-Absorber gebunden. Eine Diffusionszelle zur Herstellung von Gemischen gereinigter Luft mit Dämpfen organischer Verbindungen wurde beschrieben.

     

Adsorption from Ternary Liquid Mixtures on Partially Dehydroxylated Silica Gel

The formation of mixed adsorbed layers has been tested for ternary mixtures containing a specifically adsorbed component—acetone and binary solvent benzene +n-hepane. The specific excess adsorption isotherms from the liquid phase were measured on silica gel samples partially dehydroxylated. The competition of liquid components for silica surface is discussed on the basis of changes in the mixed solvent composition.