Effect of iodine sorption on the free volume of polycarbonate

 The effect of iodine sorption on the free volume of polycarbonate is investigated by Positron Annihilation Lifetime method. The observed results are interpreted in terms of the Charge Transfer Complex formation and precipitation of iodine at the initial and final stages of sorption, respectively. At higher levels of sorption, changes in the second lifetime and its intensity seem to suggest a conformational transformation, probably due to the net change in the amorphous-crystalline boundary regions of the polymer matrix. The free volume cavities have been predominantly occupied by I^- ₃ species and the diffusion process obeys Fick’s law. An exponential type correlation has been observed between fractional free volume and the diffusion coefficient. Received: 13 June 1996/Accepted: 20 September 1996     

A poincaré-bendixson theorem for analytic families of vector fields

We provide a characterization of the limit periodic sets for analytic families of vector fields under the hypothesis that the first jet is non-vanishing at any singular point. Also, applying the family desingularization method, we reduce the complexity of some of these sets.     

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.     

Pseudo-epitaxial C60 films prepared by a hot-wall method

We have used both reflection-geometry and grazing-incidence-geometry X-ray scattering to study thin films of C₆₀ evaporated onto mica substrates via a hot-wall technique. The growth mode yields close-packed C₆₀ planes, which are parallel to the substrate surface and which exhibit out-of-plane correlation lengths of 850 Å. In the film plane the C₆₀ is at best pseudo-epitaxial, with a 0.9° distribution of crystallite orientations, a 450 Å in-plane correlation length, and a 3.7% lattice mismatch, better than obtained by other thin film techniques but far from the accepted definition of single crystal thin film epitaxy.     

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.     

Porphyrins 34. Mass spectrometric study of ethane- and ethylene-bis-porphyrins

The mass spectral behavior of 1, 2-di (mesoetioporphyr inyl-1)- and 1, 2-di (mesooctaethylporphyrlnyl) ethanes and ethylenes, their Cu and Ni complexes, as well as Ni Schiff bases of 1, 2-di (mesooctaethylporphyrinyl)ethane complexes, under ionization by electron impact and bombardment by accelerated atoms, was studied. Peaks of molecular ions, for which the basic decomposition pathways were established on the basis of an analysis of the parent and daughter ions, were observed in the electron impact mass spectra of all these compounds.For Communication 29, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 24–29, January, 1994.     

Donor-acceptor complexes of quinoline N-oxides with boron trifluoride

Molecular n-v complexes of quinoline N-oxides with BF₃ have been studied by electronic and IR spectroscopy. In most case the donor centre is the oxygen atom of the N-oxide group.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1087–1092, August, 1994.     

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.     

O-Alkylation of furan and thiophene ketoximes in conditions of interphase catalysis in a liquid/solid system

Alkylation of 2 furanyl- and 2-thienylalkyl ketoximes with alkyl, allyl, and propargyl halides in the two phase catalytic system sol. K₂CO₃/C₆H₆/18-crown-6 at room temperature causes the formation of mixtures of E- and Z-isomers of the corresponding O-ethers with yields of 32–74%. Partial E/Z-isomerization takes place during the reaction.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 18–23, January, 1994.     

Hydroxyl-containing mesogens. Synthesis and liquid-crystalline properties of 2-o-hydroxyarylpyrimidines

We have synthesized 5-alkyl(alkoxy)-2-(o-lzydroxy-p-alkoxyphenyl)pyrimidines and considered the effect of the OH group on the inesomorphism. We have found that in binuclear o-hydroxyarylpyrimidines, an ortho OH group forming an intramolecular hydrogen bond increases T_mp, inhibits the appearance of nematic properties, and promotes the appearance of a smectic A.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 30, No. 1, pp. 90–92, January, 1994.