Influence of the sulfonate countercation on the thermal stability of nafion perfluorosulfonate membranes

We report a strong dependence of the thermal stability of Nafion® perfluorosulfonate ionomer on the nature of the counterion associated with the fixed sulfonate site. These results were obtained using thermal gravimetric analysis on a series of alkali metal and alkyl ammonium cation-exchanged Nafion films. We have found that the temperature of decomposition of Nafion is inversely dependent on the size of the exchanged cation; i.e., Nafion films show improved thermal stability as the size of the counter cation decreases. We attribute this inverse relationship of thermal stability with counterion size to an initial decomposition reaction which is strongly influenced by the strength of the sulfonate-coun-terion interaction. © 1993 John Wiley & Sons, Inc.     

Increasing the accuracy of eigenvalue computation in the spectral problem

A simple method is proposed for increasing the accuracy of computation of the eigenvalues of elliptic operators, which does not require high-order accurate schemes.Translated from Vychislitel'naya i Prikladnaya Matematika, No. 63, pp. 63–68, 1987.     

Synthesis and ring-chain isomerism of acid chlorides and amides of 2-(2-pyridyl and 2-quinolylcarbonyl) benzoic acids

The reaction of 2-(2 pyridytcarbonyl)benzoic acid with thionyl chloride affords an unexpected product of the intramolecular acylation of the pyridine nitrogen atom, namely, 6,11-dioxo-6,11-dihydrobenzo[blquinotizinium chloride. At the same time, 2-(2-quinotylcarbonyl)benzoic acid forms the expected cyclic acid chloride, namely, 3-(2-gitinotyl)-3-chlorophthalide in this reaction. Both compounds acylate ammonia and primary amines, including those with bulky alkyl groups (tert-butyl, 1-adamantyl, and 1,1,3,3-tetramethylbutyl) with the formation of 2-R-3-hydroxy-3-(2pyridyl- or 2-quinolyl)isoindolines. The protonation of the pyridine nitrogen atom of N-(1,1,3,3-tetramethylbutyl)-2-(2pyridylcarbonyl)benzamide, obtained in the open amide form, is accompanied by the closing of the isoindotinone ring; the deprotonation is accompanied by ring opening.Riga Technical University, Riga LV-1048. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 499–504, April, 1994. Original article submitted March 17, 1994.     

Electrohydraulic effect in heterodisperse water-plant systems. II. Chemical nature of the suspended particles

On the basis of the results of acid hydrolysis, chromatographic analysis of the hydrolysates, and a study of IR spectra, it has been established that the suspended particles liberated under the action of electrohydraulic shocks on heterodisperse water—plant systems consist of small fragments of the lignocarbohydrate complex of the plant tissue.     

Rhamnose orthoacetates of aconitine and imperialine

The preparation and spectral properties of rhamnose orthoacetates of aconitine and imperialine are described.Tashkent Pharmaceutical Institute. Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 743–746, September–October, 1993.     

Simultaneous determination of dexamethasone and betamethasone in pharmaceuticals by reversed-phase HPLC

Chromatographia - An HPLC method for the simultaneous determination of the glucocorticoids betamethasone and dexamethasone is described. The method based on the separation of these compounds using...     

Reversed phase behaviour of high molecular mass polystyrenes in ethyl acetate solvent mixtures

Chromatographia - The reversed phase behaviour of high molecular mass polystyrenes was investigated on C18 bonded phase columns with ethyl acetate-methanol and ethyl acetateacetonitrile mobile...     

Large Water-Soluble Cyclophanes with Convergent Intracavity Functionality

New tricyclic spacers, readily available through fourfold Mannich reaction of substituted dibenzyl ketones, were introduced into a series of ten H₂O-soluble cyclophanes with spacious preorganized cavity binding sites. These spacers provide H₂O-solubility with amine or crown-ether functionality remote from the cyclophane cavity while directing functional groups such as keto or OH groups in a precise geometrical array inside the cavity. The cyclophanes were designed to include organic substrates via a combination of apolar and specific polar functional group interactions. The X-ray crystal-structure analysis of the tritopic receptor 18 with one potential neutral-molecule and two cation-binding sites showed a large rectangular open cavity with dimensions of roughly 9 × 14 Å and a spacing of 9.7 Å between the O-atoms of two convergent C?O groups. Despite the binding-site preorganization, cyclophanes incorporating two of the new spacers did not show any substrate binding in aqueous solutions. The failure of these systems to function as receptors is mainly due to steric hindrance to important cyclophane aromatic ring-guest interactions. Also, the favorable solvation of the intracavity functionality may prevent the formation of complexes. Hybrid receptors constructed from the novel spacers and diphenylmethane units were found to bind flat aromatic substrates as well as bulky [4.2]paracyclophanes. The observed large differences in stability (ΔΔG°> 2 kcal mol^?1) of the complexes formed by three structurally closely related hybrid receptors with convergent C?O, OH or CH₂ groups and 6-hydroxynaphthalene-2-carbonitrile as guest can be explained by a strong solvation effect of the convergent functional groups on apolar inclusion complexation.     

Mechanical properties of polyester polymer-concrete

The properties of a polymer-concrete composed of polyester matrix and locally available rock aggregate are investigated. The formula of the concrete is found by an experimental-calculation approach in such a way as to attain a closer packing of the aggregate particles on the one hand, and to ensure the needed processing characteristics (placeability) of the mix on the other. It is shown experimentally that the material obtained has a rather high compression strength. Under prolonged compression loads, the polymer-concrete exhibits a noticeable creep behavior with a linear relation between the creep strains and stresses. After the action of half the ultimate load over 3000 h, the total strains exceed the instantaneous ones by 2.0 to 2.2 times. The accumulation of irreversible strains is also observed; however, their contribution to the total strain is small. It is found that the stress-strain relation can be represented by the equation of linear hereditary creep theory.Institute of Polymer Mechanics, University of Latvia, Riga, LV-1006, Latvia. Translated from Mekhanika Kompozitnykh Materialov, Vol. 35, No. 2, pp. 147–162, March–April, 1999.     

Selective photoconductivity induced in PbTe(Ga) by a local phonon mode

Selective photoconductivity at frequency ω=155 cm⁻ was discovered in PbTe(Ga) narrow-gap semiconductors at liquid-nitrogen temperatures. The corresponding energy is much lower than all characteristic energies of the electronic spectrum of the semiconductor. The effect is attributed to optical excitation of a local vibrational mode of an impurity center leading to delocalization of the electrons. Pis’ma Zh. éksp. Teor. Fiz. 63, No. 5, 342–346 (10 March 1996)