Open Access Open Access  Restricted Access Access granted  Restricted Access Subscription Access

Vol 472, No 1 (2017)

Physical Chemistry

Specific features of molecular mobility of paramagnetic probe in chiral biomimetic solutions

Kuzina S.I., Mikhailov A.I., Litvin Y.A., Stovbun S.V.

Abstract

Molecular mobility of a nitroxyl radical (as a paramagnetic probe) in methylcyclohexane (MCH) solutions of chiral biomimetic gelators—trifluoroacetylated amino alcohols (synthetic analogues of biological molecules)—has been studied by monitoring thermally induced changes in EPR spectra. The phase state of the systems has been examined by the low-temperature scanning calorimetry method. There has been found an unusual concentration and temperature dependence of probe species mobility in diluted solutions (10–2–10–3 M) of trifluoroacetylated amino alcohols with a molecular weight of no more than 200. From the temperature-induced changes in EPR spectra of the paramagnetic probe in the temperature range 170–290 K, the rotation activation energies of probe species in biomimetic solutions and in the neat solvent. The minimum radical rotation activation energy (2.1 kcal/mol) is observed in the most concentrated gelator solution, whereas in neat MCH, this energy is 3.7 kcal/mol.

Doklady Physical Chemistry. 2017;472(1):1-5
pages 1-5 views

Effect of correlations in the interaction along polymer chain on the globule structure

Astakhov A.M., Ivanov V.A., Vasilevskaya V.V.

Abstract

A special potential for interaction between polymer chain units, whose energy decreases with increasing distance s between the units as s–1, was introduced for the first time. According to Monte Carlo simulation, interactions of this type result in the formation of a globule with an equilibrium packing of domains in space. The radius of gyration of a chain segment in these globules varies with segment length according to the scaling law typical of crumpled globules.

Doklady Physical Chemistry. 2017;472(1):6-9
pages 6-9 views

High-temperature heat capacity of stannates Er2Sn2O7 and Tm2Sn2O7

Denisova L.T., Izotov A.D., Irtyugo L.A., Kargin Y.F., Beletskii V.V., Denisov V.M.

Abstract

Erbium stannate Er2Sn2O7 and thulium stannate Tm2Sn2O7 with a pyrochlore-type structure were produced by solid-phase synthesis by calcining stoichiometric mixtures of the respective oxides in air at 1473 K for 240 and 200 h. The high-temperature heat capacity of Er2Sn2O7 and Tm2Sn2O7 was studied by differential thermal calorimetry at 353–1000 K. From the experimental dependences CP = f(T), the thermodynamic functions (enthalpy change, entropy change, and reduced Gibbs free energy) of oxide compounds were calculated.

Doklady Physical Chemistry. 2017;472(1):10-12
pages 10-12 views

The role of molecular-kinetic and thermal factors in inhibition of steady detonation

Azatyan V.V., Prokopenko V.M., Abramov S.K., Smirnov N.N.

Abstract

It was experimentally shown that the reaction of the combustion of hydrogen–air mixtures in a detonation wave virtually completely (with an accuracy of 1%) occurs by a branched-chain mechanism; it is this mechanism that determines the characteristics of the detonation wave.

Doklady Physical Chemistry. 2017;472(1):13-15
pages 13-15 views

Visualization of vortex movements in a molecular dynamics model of liquid argon

Anikeenko A.V., Malenkov G.G., Naberukhin Y.I.

Abstract

A method was proposed to visualize collective displacements of particles in diffusion motion in liquids. Using this method, in molecular dynamics models of liquid argon, groups of collectively moving atoms were detected, which had the shape of long curved flows, often appearing as vortex-like structures. These structures are revealed only by considering movements of atoms over long time intervals, on the order of tens and hundreds of picoseconds, and over long distances, on the order of tens of nanometers.

Doklady Physical Chemistry. 2017;472(1):16-18
pages 16-18 views