Asymptotics of a multiple Cauchy integral with rapidly oscillating exponential

An asymptotic expansion uniform with respect to a parameter is obtained for a multiple Cauchy integral with a rapidly oscillating exponential in the integrand under the assumption that the singularity lines are in a general position.Translated fromMatematicheskie Zametki, Vol. 58, No. 2, pp. 231–242, August, 1995.The work was financially supported by the Russian Foundation for Basic Research under grant No. 94-01-00193-a.     

Magnetic phases of FexV1−x S and their electronic structure

A study has been made of the Fe_xV_1−x S solid solutions with 0<x<0.5. For the compounds with x>0.1, x-ray diffraction analysis discloses a V₅S₈ superstructure. Samples with x>0.1 are magnetically ordered at room temperature. The concentration dependences of resistivity and magnetization exhibit sharp peaks for x=0.1 and x=0.2, respectively. The main features of the structure and electronic properties have been qualitatively explained in terms of the three-band exciton-insulator model, and the maxima in resistivity and magnetization are assigned to the formation of localized magnetic moments with S=1, which become delocalized with increasing x. Fiz. Tverd. Tela (St. Petersburg) 40, 1890–1893 (October 1998)     

Effect of a Competing n Donor on the Rate of AlCl3-Catalyzed Diels-Alder Reaction of 9,10-Dimethylanthracene with Maleic Anhydride

The catalytic effect of AlCl₃ on the Diels-Alder reaction of 9,10-dimethylanthracene with maleic anhydride is dramatically weakened on addition of a competing n donor, dibutyl ether. The n,v complex of aluminum chloride with dibutyl ether is considerably more stable than the complex with maleic anhydride; therefore, the catalytic effect is suppressed even at comparable concentrations of these n donors.     

Photosensitization of electronic transitions by dye molecules in systems consisting of a semiconductor and adsorbed molecules of p-benzoquinone

Electrophysical methods and ESR measurements have been used to investigate the changes, photosensitized by molecules of rhodamine B (RB), in the charge states of electron traps created by molecules of p-benzoquinone (pBQ) in the Ge/GeO₂ system. The results obtained in studying the quenching of fluorescence of RB molecules indicate that the photodestruction of electron traps is due to transfer of electronic excitation energy traps is due to transfer of electronic oxidation energy from the RB molecules to charged complexes formed upon adsorption of the pBQ. In order to select optimal conditions for recharging of such complexes, a study has been made of the relationship between the relative change in ESR signal and the concentration of adsorbed RB molecules.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 5, pp. 545–550, September–October, 1989.     

Activation and Reaction Volumes for [4+2] and [3+2] Additions Involving Maleic Anhydride

The partial molar volumes of reactants and products of the [3+2] addition of C-(p-nitrophenyl)-N-phenylnitrone to maleic anhydride and of the [4+2] addition of 9,10-dimethylanthracene to the same dienophile were determined, and the reaction volumes were calculated. A new method was suggested for determining the reaction volume. The activation volumes of both reactions were calculated from the dependences of the reaction rates on the external pressure. The volume parameters of the reactions involving the reagents of close size are close. The ratios of the activation volumes to the reaction volumes are unity, which suggests a common concerted mechanism of the reactions. Factors that could be responsible for significant changes in the absolute values of the reaction volume parameters are discussed.     

Liquid chromatography of benzene derivatives on a porous methacrylate copolymer containing epoxy groups

Summary The retention of benzene derivatives with nonpolar and polar substituents on a porous methacrylate copolymer containing epoxy groups using both nonpolar and polar eluents was investigated. When n-hexane is used as the eluent, the retention of n-alkylbenzenes and polymethylbenzenes is weaker than that of benzene. In the case of benzene derivatives containing polar functional groups their capacity ratios (k) on this porous polymer increases approximately linearly with the increase of the adsorbate molecules dipole moment. The retention characteristics of the methacrylate copolymer were compared with that of a styrene-divinylbenzene copolymer and silica gels with a hydroxylated surface and with a surface modified by chemically bonded alkylsilyl groups.     

Diels—Alder reaction. Effect of internal and external factors on the reactivity of diene—dienophile systems

The key factors influencing the Diels—Alder reaction rate at ambient and elevated pressures were elucidated using data on the reactivity of various diene—dienophile systems in usual and Lewis acid-catalyzed Diels—Alder reactions, the reaction enthalpy, complex formation, dissolution, and solvation, and the donor-acceptor properties of the reactants. It was found that taking account of both the orbital interaction energy and the balance of bond rupture and formation energies allows correct prediction of the reaction rate in the absence or in the presence of Lewis acids.     

Photosensitive molecular tweezers 3. Synthesis and homoditopic complex formation of a bisstyryl dye containing two crown-ether fragments with diammonium salts

A new molecular tweezers, viz., bisstyryl dye containing two 18-crown-6-ether moieties and one p-phenylenedimethylene spacer group, was synthesized. Complex formation of this dye and a model monostyryl dye with ions EtNH₃ ⁺ and NH₃ ⁺(CH₂)_nNH₃ ⁺ (n = 2−6) in MeCN was studied using spectrophotometry and ¹H NMR spectroscopy. The homoditopic bisstyryl dye and diammonium salts form strong supramolecular complexes with pseudocyclic structure.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 656–662, March, 2005.     

Diels-Alder reaction volumes in the solid state and solution

The densities of anthracene, tetracyanoethylene, maleic anhydride, N-phenylmaleineimide, trans, trans-1,4-diphenylbuta-1,3-diene, and their Diels-Alder adducts were measured in the solid state and in solution at 25 °C. The reaction volumes in the solid state were calculated from the difference in molar volumes. They turned out to be low, close to each other (–4 to –11 cm³ mol^–1), and slightly different from the reaction volumes (–8±1 cm³ mol^–1) calculated from the van der Waals radii. The reaction volumes in solutions (–15 to –32 cm³ mol^–1) were found from the difference in partial molar volumes of the reactants in dioxane, acetonitrile, and 1,2-dichloroethane, The experimental Diels-Alder reaction volumes in solution are determined not only by the formation of new bonds in an adduct: a considerably higher contribution (to 75%) is made by a change in the volume of intermolecular empty spaces in solution on going from reactants to adducts.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2386–2390, November, 2004.