Phraseological system of Russian : how to train foreigners?

The studying of the phraseological system of Russian supposes not just the knowledge or the acquisition of abilities to use it but the development of pupils to use other languages for communication. The specifics of the perception of phraseological units are defined by the native language and by the second and the next following foreign languages. The figurative structure of the native language therefore accounting of the native language of pupils, features the culture of language, becoming the important didactic principle for the Russian phraseological units. For training in the Russian phraseological units, it is necessary to use two main types of means: the natural language environment with all its extralinguistic components and various supportive applications creating more or less expressed illusion of familiarizing with the natural language environment. A necessary element of work on the phraseological system of Russian is the semantization of phraseological units. In disclosure of value of a phraseological unit, the image defining its lexical - semantic structure is the key. The work on phraseological units by foreign audience has to assume disclosure of value of a phraseological unit by means of interpretation, transfer and a semantic guess and fixing based on specially developed exercises and texts.peer-reviewe

An experimental and quantum-chemical study of the Raman spectra and rotational isomerism of thiophosphites (RS) n PCl3 - N (R = Me, Et; N = 1, 2)

The Raman spectra of different conformations of CH3SPCl 2, C2H5SPCl2, and (C 2H5S)2PCl are studied within the framework of the density functional theory (B3LYP/6-31G*and B3LYP/6-31+G*) using the method of scaling of force fields. Comparison of the calculated and experimental spectra makes it possible to interpret the latter and to establish the existence of trans and gauche conformers of these molecules, which are formed due to internal rotation about the P-S and S-C bonds. This comparison also shows that, for the prediction of the degrees of depolarization of Raman lines to be correct, it is necessary to introduce diffuse functions into the basis set. © Nauka/Interperiodica 2006

Thermal stability of primary and secondary phosphine oxides formed as a reaction of phosphine oxide with ketones

© 2016 Taylor & Francis Group, LLC.We present the study of reactivity of electrochemically generated in situ from white phosphorus P4 phosphine oxide H3PO toward various ketones (acetone, methylethylketone, methyl-n-propylketone). This interaction was found to give a selective formation of mono- and bis-(α-oxyalkyl)phosphine oxides RRʹC(OH)P(O)H2 (1) and (RRʹC(OH))2P(O)H (2) where R = Me; Rʹ = Me, Et, n-Pr. Thermal properties of the formed primary and secondary phosphine oxides have been studied and quantum chemical calculations of thermodynamic stability of these compounds were performed

First neutral dinuclear cobalt complex formed by bridging [μ-O2P(H)R]- ligands: Synthesis, X-ray crystal structure and quantum-chemical study

© 2015 Mendeleev Communications. Published by Elsevier B.V. The reaction of cobalt dibromide hexahydrate with 2,2′-bipyridine (bpy) and 9-anthrylphosphinic acid AntP(O)(OH)H (Ant = 9-anthryl) leads to the first example of a neutral dinuclear cobalt(ii) complex {Co2Br2[μ-O2P(H)Ant]2(bpy)2} formed by two bridging [μ-O2P(H)Ant]- ligands. The complex has been characterized by X-ray diffraction analysis and quantum-chemical calculations

Synthesis, X-ray crystal structure and quantum-chemical study of new dinuclear cobalt complex {Co2[mmm-O2P(H)Mes] 2(bpy)4}Br2

The reaction of cobalt dibromide hexahydrate with 2,2'-bipyridine (bpy) and mesitylphosphinic acid MesP(O)(OH)H (Mes = = 2,4,6-trimethylphenyl) under solvothermal synthesis conditions leads to a new dinuclear cobalt(ii) complex {Co2[μ-O2P(H)Mes]2- (bpy) 4}Br2 formed by two bridging {μ-O2P(H)Mes}- ligands. X-ray crystal structure analysis of the complex displayed that cobalt ions have distorted octahedral coordination and are doubly bridged by two mesitylphosphinato ligands. © 2013 Mendeleev Communications. All rights reserved

IR and NMR spectra, intramolecular hydrogen bonding and conformations of mercaptothiacalix[4]arene molecules and their para-tert-butyl-derivative

It is demonstrated that the introduction of p-tert-butyl groups dramatically influences the conformational behaviour of the mercaptothiacalix[4] arene molecules. Quantum-chemical computations in combination with IR and NMR spectroscopy prove that, in contrast to closely related calixarenes, the 1,3-alternate becomes a dominant conformer of p-tert-butyl-mercaptothiacalix[4] arene not only in crystal, but also in solutions and in vacuum. It is shown that the title molecules form essentially non-cooperative intramolecular hydrogen bonds: their SH groups are intramolecularly H-bonded solely to the sulfide groups bridging thiophenolic units. The enthalpy of this bonding, evaluated from Iogansen's rule, amounts to ca. 1.5 kcal mol-1 per one SH•••S bond, which about four times smaller than the enthalpies of cooperative intramolecular H-bonds formed by related calixarenes and thiacalixarenes. © 2007 Springer Science+Business Media B.V

Conformational analysis of mono-and bis(dimethoxyphosphoryl)benzenes

Conformational analysis of mono-and bis(dimethoxyphosphoryl)benzenes with substituents in the benzene ring was performed by the method of dipole moments, IR spectroscopy, and quantum-chemical calculations (DFT B3LYP/6-31G*). Comparison of all calculated and experimental data shows that the compounds studied exist as equilibrium mixtures of conformers with preferred gg orientation of the phosphoryl and methoxy groups. © Pleiades Publishing, Inc., 2006

Complex formation of d-metal ions at the interface of Tb III-doped silica nanoparticles as a basis of substrate-responsive TbIII-centered luminescence

The complex formation of d-metal ions at the interface of Tb III-doped silica nanoparticles modified by amino groups is introduced as a route to sensing d-metal ions and some organic molecules. Diverse modes of surface modification (covalent and noncovalent) are used to fix amino groups onto the silica surface. The interfacial binding of d-metal ions and complexes is the reason for the TbIII-centered luminescence quenching. The regularities and mechanisms of quenching are estimated for the series of d-metal ions and their complexes with chelating ligands. The obtained results reveal the interfacial binding of CuII ions as the basis of their quantitative determination in the concentration range 0.1-2.5 μM by means of steady-state and time-resolved fluorescence measurements. The variation of chelating ligands results in a significant effect on the quenching regularities due to diverse binding modes (inner or outer sphere) between amino groups at the interface of nanoparticles and FeIII ions. The applicability of the steady-state and time-resolved fluorescence measurements to sense both Fe III ions and catechols in aqueous solution by means of Tb III-doped silica nanoparticles is also introduced. © 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

IR and NMR spectra, intramolecular hydrogen bonding and conformations of para-tert-butyl-aminothiacalix[4]arene in solid state and chloroform solution

It is demonstrated that dissolution of aminothiacalix[4]arene in chloroform results in transformation of 1,3-alternate conformation, adopted in single-crystal and bulk polycrystalline solids, to the pinched-cone form. This conformer is stabilised by the intramolecular hydrogen bonds of two distal amino-groups acting as H-donors with another two amino moieties that appear as H-acceptors. The H-bonds cause quite small (ca. 10-20 cm-1) red shift of the IR bands of the NH2 stretching vibrations, which suggests rather weak NH⋯N hydrogen bonding. This latter is sufficient to stabilize the pinched-cone conformation in the chloroform solution, but the energy gap between the pinched-cone and other conformations is small, and solid-state intermolecular forces easily overcome it, leading to realisation of the 1,3-alternate conformer. The comparison of the DFT computed and experimental vibrational and NMR spectra demonstrates good quality of present quantum-chemical computations, allows complete interpretation of the spectra and reveals simple IR and NMR spectroscopic markers of the conformers of aminothiacalix[4]arenes. © 2009 Elsevier B.V. All rights reserved

Vibrational spectra, co-operative intramolecular hydrogen bonding and conformations of calix[4]arene and thiacalix[4]arene molecules and their para-tert-butyl derivatives

The IR and Raman spectra and conformations of calix[4]arene, thiacalix[4]arene and their p-rerf-butyl derivatives have been analysed within the framework of scaled quantum mechanics (SQM). It is shown that the introduction of four p-tert-Bu groups into the calixarene molecules influences the relative energies of their conformers and the enthalpy of the cooperative intramolecular H-bonding (ΔHintra) almost negligibly. ΔHintra, evaluated from Iogansen's rule, amounts to ∼ 26-28 kcal mol-1 for the calixarenes and ∼20-21 kcal mol -1 for the thiacalixarenes, which essentially exceeds the enthalpies of non-cooperative H-bonds formed by related phenols. As a result of this strong bonding, bands of stretching, bending and torsion vibrations of an eight-membered cyclic system (OH ⋯)4 arise, e.g., two δ(OH)4 bands are observed in the IR spectra of the most highly symmetric C4 cone conformations of calix[4]arene and thiacalix[4]arene. The "duplication" of the number of OH infrared bands is a good new indicator of cooperativity of intramolecular H-bonding of the calixarenes. © The Royal Society of Chemistry 2005