Home – Home – Jornals – 2013 number 3

The article offers the approach to determination of optimal penalty value for dominant position abuse. The approach is evaluated by the example of coal industry agents of the Russian Federation.

The actuality of scientific approach to criminalistic characteristics of crimes is defined by its value to the investigation technique of illicit traffic in drastic or poisonous substances for the purpose of sale. The analysis of criminalistic characteristics of the mentioned type of crimes is the main research trend. Its specifics is revealed on the basis of fundamental notion – “criminalistic characteristics of crimes”. The article offers a structure of illicit traffic in drastic or poisonous substances for the purpose of sale, interrelations between its structural elements are defined. Their interaction by the examples from practice of preliminary investigation agencies is dramatically illustrated.

The article offers requirements that must be satisfied for efficiency at implementation of restructuring activities. Main aspects of enterprise activity that should be considered at forming of the restructuring project are defined. Main and auxiliary conditions that must be observed to consider mandatory aspects at the elaboration of restructuring activities are revealed on the basis of conducted research.

Methodology of in situ investigations aimed at the studies of heterogeneous catalytic reactions is presented. The advantage of this approach in comparison with ex situ studies is demonstrated with a number of examples. The outlooks and possibilities of the application of various physical methods in the in situ mode are considered.

Modification of the oxide surface of aluminium oxide with oxalate complexes of aluminium was carried out, followed by thermal treatment for the purpose of varying the ratio between the functional groups on the surface (ОН groups, Lewis acid centres). It was established that the modification of γ–Al₂O₃ causes a 1.5-fold increase in the amount of adsorbed platinum (IV) complexes and the fraction of these complexes strongly bound with the surface of the support. The effect of γ–Al₂O₃ surface modification on the catalytic properties of the system Pt/Al₂O₃ was demosntrated. It was shown that an increase in the fraction of platinum forms strongly bound with the support causes an increase in the content of methylcyclopentane in the products of n–hexane isomerization and an increase in the selectivity of the formation of propylene in propane transformations.

Modern approaches to the development of ecologically and economically acceptable methods for obtaining a number of industrially essential products are considered. The promising character of the application of phase-transfer catalysis method for reactions proceeding in liquid two-phase systems with the use of ecologically favourable oxidizing agent – hydrogen peroxide – was demonstrated. Results of integrated studies of the structural characteristics of tungsten peroxopolyoxocomplexes formed in the interaction of the aqueous solutions of phosphotungstic heteropolyacid with hydrogen peroxide by means of EXAFS, Raman and IR spectroscopy are presented. The synthesized catalysts Q₃{PO₄[WO(O₂)₂]₄}, where Q₃ is a quaternary ammonium cation, were tested in the reactions of oxidation of organic substrates with 30–35 % H₂O₂ solutions.

The review is devoted base-catalyzed intramolecular cyclization of ammonium salts containing β,γ-unsaturated groups alongside with various enyne fragments. This process results in the formation of polynuclear isoindolinium salts and in the transformation (recyclization) of those containing the hydroxymethyl group at the position 4 in the aromatic ring.

There were investigated two variants of NaCl isolation from the solutions of human exometabolite mineralization and plant wastes, based on the fractional crystallization of salts via evaporation and the low solubility of NaCl in concentrated HCl, respectively. It has been established that owing to preferential dissolution of the impurities in the concentrated HCl, from the mineralized solutions one could recover 99 % of NaCl contained therein, whose purity of which is not worse with respect to the standard food grade salt. The methods for proposed processing the mineralized solutions allow one to involve NaCl and H₂O into the mass exchange within closed environments.

With the use of HPLC technique, studies on the amino acid composition of human bone tissue within the age range of 30–79 years were performed. Gender-features concerning the qualitative and quantitative amino acid content have been revealed. It is demonstrated that the clinical course of coxarthrosis does not lead to significant changes in amino acid composition of human bone tissue.

Organochlorine wastes generated in the production of epichlorohydrin, and lignin could be co-processed to obtain the sulphur-containing derivatives. For this purpose, the wastes of chloroorganic synthesis and hydrolytic lignin chlorinated under mild conditions should be entered into the reaction with sulphur in the form of sodium polysulphides. The overall process is cost-efficient due to the fact that it provides an almost complete conversion of organochlorine waste disposal, sulphur compounds as well as lignin binding. The condensation products obtained were tested as additives for modifying bitumen and demonstrated a good processability.

The dynamics of thermolysis was studied for the bituminous sandstone taken from the Bayan-Erkhet deposit (Mongolia). It has been demonstrated that the thermolysis procedure could be used for the isolation of bituminous component from these raw materials to obtain valuable intermediates for coal chemistry and motor fuels.

The results of research work are reported concerning the thermal decomposition of coal species from the Ulugh and Chadan beds of the Kaa-Khem site of the Tuva deposit as well as an effect of coal activation on the decomposition process. Potentiality is demonstrated for briquetting the coal after removing gaseous and light liquid fractions from the material.

An alternative gas phase nitration process was investigated wherein the reaction between an aromatic substrate (benzene/toluene) and a nitrating agent (either a 68 mass % HNO₃ aqueous solution, or a mixture of nitrous gases) occurs on a fixed-bed solid acidic catalyst. There have been studied physicochemical properties (elemental composition, pH, crystallinity) and catalytic properties inherent in the samples of naturally occurring zeolites taken from the deposits of Siberia and the Far East. An effect of zeolite preliminary treatment (calcination and acid extraction method) exerted on the activity thereof was investigated. It has been demonstrated that the highest activity is exhibited by a sample with the highest concentration of Bronsted acid sites (99 µmol/g according to NH₃ adsorption), taken from the Kulikovo deposit (the Amur Region). The productivity of the sample amounted to 161 mg/(g_cat · h).

Studies were performed concerning the features of soil ecological, microbiological and biochemical properties under influenced by the emissions of aluminum plants in Siberia. It has been found that the anthropogenically transformed soils of sub-taiga influenced by water-soluble fluoride species (10–20 MPC) cause the greatest inhibition of actinomycetes and chemoorganotrophic asporogenous bacteria. The steppe chernozem under the influence of fluorine (1–4 MPC) demonstrates a decrease in the level of biochemical activity.

Integrated studies of ion exchange extraction of tungsten was carried out in application to the carbonate solutions of autoclave leaching of raw material with low tungsten content. Anionite and desorbent for tungsten extraction were chosen. The integrated technology of processing tungsten-containing raw material was proposed, resulting in obtaining metal tungsten, with the possibility of regeneration of the treating reagent sodium carbonate.

The composition and structural features of the resin-asphaltene macromolecular fragments inherent in the substances from the Usinsk oilfield were investigated. It has been demonstrated that they contain ether and/or ester groups. Nitrogenous bases in the form of supramolecular structures are present only in the structure of the resinous components.

Changes of the quantitative and qualitative characteristics of peat components (bitumen, lignin, cellulose, humic acids) under cavitation action of aqueous alkaline media are considered. It was demonstrated that the cavitation treatment of peat in alkaline solutions involves the structural rearrangement, changes of separate fragments of macromolecules. As a result, additional amount of humic acids is formed. To obtain humic acids, it is preferable to use the aqueous solution of ammonia as the base. In water-ammonia medium, nitrogen fixation occurs with the participation of all the components of humate–carbohydrate complex.

By the example of the structure of phenanthrene the character of the H–H interaction is studied by non-empirical quantum chemical methods. The calculations performed confirm Bader’s conclusions about the attractive character of the H–H interaction, which were made based on the QTAIM analysis, and disprove the repulsive character of the above interaction, which was derived from the EDA procedure.

DFT and HF methods using the PC GAMESS-Firefly program are employed to calculate the spatial and electronic structures of molecules: alkoxy derivatives of aluminum. By NBO and AIM methods the main characteristics of Al–O, C–O, and Al–X bonds in these molecules are determined. It is shown that Al and О atoms interact with each other as atoms with closed shells. The С–O bonds are close to covalent, whereas the Al–X bonds are the intermediate type bonds.

By the density functional method (B3LYP/6-31++G(d,p)) optimal structures of proton hetero and homo disolvates involving water molecules, ethyl formate, methyl acetate and products of their hydrolysis are calculated. The data on the structure of these ions and the strength of their H bonds are analyzed together with the results of a similar calculation previously performed for methyl formate. It is shown that in proton solvation by two molecules present in the solution during the hydrolysis of ethyl formate, methyl acetate, and methyl formate stable (X⋯H⋯X)⁺ or (X⋯H⋯Y)⁺ particles form. Structural and energy parameters of their O⋯H⋯O bridges obey the same regularities and are mainly determined by a difference in the proton affinity of X and Y molecules. Calculation results are compared to the data of a number of experimental studies of the acid hydrolysis of esters.

The geometries of ten benzenoid energetic materials are fully optimized by employing B3LYP and B3P86 methods with the 6-31G** basis set. Bond dissociation energies (BDEs) for the removal of the NO₂ group in benzenoid molecules are calculated at the same level. The calculation results show that the insertion of an electron withdrawing group increases the stability of the molecules, while the insertion of an electron donating group reduces the stability of the molecules. In addition, the relationship between the impact sensitivities and the weakest BDE values is examined. There exists a good linear correlation between the impact sensitivity and the ratio of the BDE value to the molecular total energy.

As a result of a joint interpretation of mass spectra and gas chromatographic retention indices more than ten products of free radical chlorination of methyl-tert-butyl ketone are identified. They contain from one to six chlorine atoms in the molecule and were not previously characterized either by mass spectrometric or chromatographic reference data. It is found that retention index increments corresponding to a gradual increase in the number of chlorine atoms in the molecule per unit are non-additive and vary in wide ranges (from 53 i.u. to 219 i.u.), which does not hinder the use of separate elements of additive schemes for the estimation of the indices of products of such non-regioselective reactions.

X-ray photoelectron spectroscopy (XPS) and density functional theory are employed to study the electronic structure of octasilsesquioxanes (RSiO_1.5)₈ with vinyl and phenyl terminal groups. Quantitative compositions determined from the XPS data are close to those estimated by empirical formulas. Narrow spectral lines corresponding to ionization from C1s core levels indicate similar chemical states of carbon atoms for both compounds. Experimental data are confirmed by close calculated values of effective charges on carbon atoms when polarization functions are included in the basis set and also by small energy ranges of core level electrons. The valence spectral region is interpreted based on the calculated energy values of electronic levels with regard to the density of states and ionization cross-sections.

Reaction of dinuclear platinum(II) sulfido complex [Pt₂(µ-S)₂(PPh₃)₄] with 1,3-propanesultone gives the novel zwitterionic monoalkylated thiolate complex [Pt₂(µ-S){µ-S(CH₂)₃SO₃}×(PPh₃)₄], which was characterized by NMR spectroscopy, electrospray ionisation mass spectrometry, and a single crystal X-ray structure determination. Crystals are monoclinic, space group P2(1)/ c with unit cell dimensions a = 16.8957(3) Å, b = 15.5031(3) Å, c = 28.0121(5) Å, β = 99.780(1)°, for Z = 4.

Thermodynamic characteristics of aqueous linear diol solutions are calculated. These data are used to identify regularities in the variations of the structural properties of the mixtures being studied. The correlation between the entropy and enthalpy characteristics of water–diol systems with excess packing coefficients is evidence that the structural and energy properties of aqueous linear diol solutions are determined by universal interactions. The form of the concentration dependences of the solvation enthalpies and entropies of noble gases in water–linear diols mixtures is determined by the reorganization component and is attributed to the destruction of the H bond network of water, which results in the formation of the most densely packed solutions in the medium range of compositions.

The dependence of the standard partial volumes of glycine, a-alanine, and serine on the ionic strength of aqueous sodium chloride and sulfate solutions is modeled by the extended Masson equation: V⁰ = V_w⁰ + AI^0,5 + BI. The error of less than 0.2 cm³/mol is a result of using five values of the А and В parameters: the two values of А are determined by the type of salt and the three values of В by the type of amino acid. A new variation of the additive-group approach is proposed for ΔV⁰ = V⁰ - V_w⁰. The partial volumes of the СН₃ group (a-alanine) and the СН₂ group (serine) are found not to depend on the salt concentration. The partial volume of the СН₂ group of glycine grows with concentration. The structural characteristics of the hydrated complexes of the NH₃⁺ and COO^- groups are calculated: the hydration numbers, the molar volumes of water inside and outside the hydration sphere, and the intrinsic volume of NH₃⁺ in COO^- in solution. Given the same ionic strength, the aqueous sodium sulfate solution produces a somewhat stronger dehydration of the charged groups.

The monoclinic modification of ZrF₄×3H₂O, isostructural to HfF₄×3H₂O, is synthesized and structurally studied for the first time. Unlike the triclinic modification of ZrF₄×3H₂O with a dimeric structure, the synthesized compound has a polymer structure formed from infinite chains composed of ZrF₆(H₂O)₂ groups sharing F…F edges. The crystal structure of HfF₄×3H₂O, previously determined by the photo method, is refined. The refined data on the geometric characteristics of the coordination polyhedron of the Hf atom and the system of hydrogen bonds in the structure are obtained.

Single crystals of a new compound containing triphenylguanidinium and bis(dicarbollide)nickel(III) [C(NHC₆H₅)₃][Ni(B₉C₂H₁₁) ₂] are obtained and analyzed by LOW-TEMPERATURE. Crystallographic data are: C₂₃H₄₀B₁₈N₃Ni, M = 611.87, monoclinic system, space group P2₁/с, unit cell parameters: a = 21.9085(5) Å, b = 19.9294(4) Å, c = 14.8721(4) Å, β = 91.4033(9)°, V = 6491,5(4) ų, Z = 8, d_x = 1.252 g/cm³, T = 100 K, F(000) = 2536, μ = 0.621 mm^–1. The structure was solved by direct and Fourier methods and refined by the full matrix least squares technique in the anisotropic/isotropic (for H atoms) approximation up to the final factor R₁ = 0.053 for 10429 I_hkl ≥ 2σ_I (Bruker X8 APEX diffractometer, MoK_α radiation). It contains two independent [C(NHC₆H₅)₃]⁺ cations with different conformations and two [Ni(B₉C₂H₁₁)₂]^– anions with the same transoid conformation. Three types of weak intermolecular interactions are found: N–H^δ+⋯^δ–H–B; C–H⋯π between the H(C) atoms of cluster anions and delocalized π systems of Ph rings of cations; π⋯π interactions of Ph rings of cation 2 with each other.

A new cadmium(II) complex with (1'H-[2,2']Biimidazoly-1-yl)-acetic acid (HBDAC) [Cd(BDAC)₂(H₂O)₂]×H₂O is synthesized and structurally characterized, which crystallizes in the monoclinic system, space group P2₁/c , a = 8.465(3) Å, b = 14.164(5) Å, c = 11.294(3) Å, α = 90°, β = 127.405(17)°, γ = 90°, Z = 2. The [Cd(BDAC)₂(H₂O)₂]·H₂O units are further bridged by O—H^…O, N—H^…O, C—H^…O hydrogen bonds, π—π stacking and C—O^…π interactions, generating a three-dimensional supramolecular structure. In addition, luminescence measurements reveal that complex 1 exhibits strong fluorescent emission in the solid state at room temperature.

Molecular and crystal structures are determined for amino-substituted nitronyl nitroxide 1, the products of its subsequent oxidation, acylation, and reduction: zwitter-ions 3a, 3b and salts K(4b) and K₂(4b)(CF₃CO₂).

The crystal and molecular structure of potassium thiobarbiturate C₄H₃KN₂O₂S (C₄H₄N₂O₂S–2-thiobarbituric acid, H₂TBA) is determined. Crystallographic data for KHTBA are as follows: a = 11.2317(17) Å, b = 3.8687(6) Å, c = 14.557(2) Å, β = 97.448(4)°, V = 627.18(17) ų, space group P2/c , Z = 4. Each potassium ion is linked with four oxygen atoms and two S atoms forming a distorted octahedron. N–H⋯O and C–H⋯S hydrogen bonds form a branched three-dimensional network. The structure is also stabilized by the π–π interaction of heterocyclic HTBA^– ions.

A 4,4'-bipyridine Zn(II) complex [Zn(4,4'-bipy)₂(H₂O)₄](ClO₄)₂×4(4,4'-bipy) is synthesized, characterized by elemental analysis, IR, ¹H NMR, ¹³C NMR spectroscopy, and studied by X-ray crystallography. The compound forms monomeric units as a result of unusual unidentate coordination of 4,4'-bipy ligands. The thermal stability of the compound is studied by thermal analyses. Furthermore, the complex is luminescent with emission maxima at 329 nm in the methanol solvent. Different sizes of zinc(II) oxide nanoparticles are prepared by calcination of the [Zn(4,4'-bipy)₂(H₂O)₄](ClO₄)₂×4(4,4'-bipy) compound at two different temperatures. These nanostructures are characterized by X-ray powder diffraction and scanning electron microscopy.

The crystal structure of {aquaimidazole[2-(2-carbamoylhydrazone)-propionato]}copper(II) nitrate [Cu(L)Im(H₂O)]NO₃ (I), where HL is the semicarbazone of pyruvic acid, Im is imidazole, is dtermined. The crystal structure of I contains two independent complexes IА and IВ in which copper atoms coordinate once deprotonated tridentate НL, imidazole, and water molecules. Outer spheres of the complexes contain nitrate ions. In the compounds studied the coordination polyhedron of the copper atom is a distorted tetragonal pyramid. Its base is composed of carboxyl and carbamide oxygen atoms, azomethine nitrogen of monodeprotonated HL molecules, and the imidazole nitrogen atom. In the crystal, nitrate ions and imidazole molecules link the complexes via hydrogen bonds into 2D networks parallel to the (010) plane. These networks in turn are in pairs arranged into layers along the [010] direction due to hydrogen bonds between water molecules and oxygen atoms of nitrate ions, and also by water molecules and O3 atoms of the neighboring 2D networks. In the crystal, the π–π stacking interaction is observed between the imidazole rings from different layers and there is also a N–O⋯Cg (π ring) interaction inside the layers.

Two new isostructural methoxide-bridged dimeric oxovanadium(V) complexes [VO(L¹)(OMe)]₂ (1) and [VO(L²)(OMe)]₂ (2), where L¹ and L² are the deprotonated forms of 3-bromo- N'-[1-(2-hydroxyphenyl)ethylidene]benzohydrazide (H₂L¹) and 3-chloro-N '-[1-(2-hydroxyphenyl)ethylidene]benzohydrazide (H₂L²) respectively, are synthesized and characterized by elemental analyses, IR spectra, and single crystal X-ray determination. Both crystals crystallize in the triclinic space group P-1. For 1, a = 7.5237(15) Å, b = 10.846(3) Å, c = 11.195(3) Å, α = 84.143(3)°, β = 72.244(3)°, γ = 77.869(3)°, V = 849.9(4) ų, Z = 1, R₁ = 0.0634, wR₂ = 0.1373. For 2, a = 7.493(2) Å, b = 10.740(3) Å, c = 11.109(3) Å, α = 84.569(2)°, β = 71.783(2)°, γ = 79.822(2)°, V = 835.0(4) ų, Z = 1, R₁ = 0.0511, wR₂ = 0.1076. Each V atom in the complexes is octahedrally coordinated.

Two new zinc(II) complexes [ZnL(N ₃)]×BF ₄ (1) and [ZnBrL]×BF ₄ (2), derived from the tetradentate Schiff base ligand N,N'-bis(1-pyridin-2-yl-ethylidene)propane-1,3-diamine (L), are prepared and characterized by physicochemical methods and single crystal X-ray crystallography. The crystal of (1) is triclinic: space group P-1, a = 8.593(1) Å, b = 8.752(1) Å, c = 13.393(2) Å, α = 97.153(1)°, β = 93.046(1)°, γ = 91.577(1)°, V = 997.4(2) ų, Z = 2. The crystal of (2) is triclinic: space group P-1, a = 8.351(1) Å, b = 8.956(1) Å, c = 13.139(2) Å, α = 92.716(1)°, β = 94.241(2)°, γ = 95.016(1)°, V = 974.8(2) Å ³, Z = 2. The geometries of the penta-coordinated zinc atoms in both complexes are intermediate between the square pyramid and the trigonal bipyramid having the Addison parameters of 0.39 and 0.47 respectively. The syntheses of the complexes show distinct preference for the anions in the order Br^– >N₃^–> CH₃COO^–.

bis-Isonicotinoyl hydrazone of 2,5-diformylpyrrole existing in the crystal in the form of a tetrahydrate of the hydrazone tautomeric form is synthesized and its structure is described. In the crystal, an infinite three-dimensional network of hydrogen bonds is formed by hydrazone molecules. The neighboring hydrazone molecules are bonded by intermolecular π stacking interactions. A quantum chemical calculation of the geometry and total energy of possible tautomers in vacuum and an aqueous solution is performed.

We study the interaction of dialkyl substituted and cyclic cadmium dithiocarbamates with [AuCl₄]^– anions in 2M HCl medium. The state of the chemisorbents upon contact with AuCl₃ solutions is controlled by ¹¹³Cd MAS NMR spectroscopy. The result of the heterogeneous reactions involving chemisorption binding of gold(III) from the solutions and partial ion exchange is the formation of heteropolynuclear gold(III)–cadmium complexes. The crystal and molecular structure of the acetone-solvated form of polymeric bis-(N,N-diethyldithiocarbamato-S,S') gold(III) hexachlorodicadmate is identified by single-crystal XRD. The main structural moieties of the compound are complex [Au{S₂CN(C₂H₅)₂}₂]⁺ cations and [Cd₂Cl₆]^2– anions. The structural self-organization of the complex at the supramolecular level is attributed to the secondary Au⋯S bonds between neighboring isomeric complex gold(III) cations; the bonding results in the formation of linear polymer ([Au{S₂CN(C₂H₅)₂}₂]⁺)_n chains, with [Cd₂Cl₆]^2– anions alternating to the right and left of the chains.

New (C₁₇H₂₀FN₃O₃)₂[CoCl₄]₂×3H₂O (I) and C₁₇H₂₀FN₃O₃[CoCl₄]×H₂O (II) compounds, where C₁₇H₁₈FN₃O₃ is ciprofloxacin (CfH), are synthesized and their crystal structures are determined. Crystallographic data for I: a = 18.441(5) Å, b = 9.030(3) Å, c = 27.551(8) Å, V = 4588(4) ų, space group Pca2₁, Z = 4; for II: a = 9.305(3) Å, b = 9.885(3) Å, c = 12.999(4) Å, α = 82.782(4)°, β = 72.954(4)°, γ = 89.736(4)°, V = 1133(1) ų, P–1 space group, Z = 2. Both structures contain CfH₃²⁺ ion pairs bonded by the π–π interaction. Additionally, in the crystal of I there is a stacking interaction between the π clouds of aromatic rings and hydrogen atoms of the cyclopropyl group linking the pairs of molecules with each other. The structure of the centrosymmetric crystal of triclinic phase II is also formed from CfH₃²⁺ ion pairs bonded by the π–π interaction, which, in this case, are not independent because they are related by the symmetry center. Hydrogen bonds form a branched three-dimensional network linking the CfH₃²⁺ and CoCl₄^2– ions and water molecules.

A new trinuclear Ni(II) complex {[NiL(DMF)]₂(OAc)₂Ni}×2DMF (H₂L = 4,4'-dichloro-2,2'-[(1,3-propylene)dioxybis(nitrilomethylidyne)]diphenol) is synthesized and characterized by elemental analyses, IR spectra, UV—Vis spectra and X-ray crystallography. The results show that the Ni(II) complex consists of three Ni(II) ions, two tetradentate (μ-L)^2– units, two coordinated μ-acetate ions, two coordinated DMF molecules, and two crystallization DMF molecules. All hexacoordinated Ni(II) ions of the complex have a slightly distorted octahedral geometry. The crystal packing of the Ni(II) complex reveals a notable feature of this structure: the formation of an infinite supramolecular 2D layered structure by virtue of intermolecular C—H⋯O hydrogen bonding.

Phthalazinylhydrazone of 2-formylpyrrole is synthesized, the values of ionization constants are determined, and quantum chemical calculation of the geometry and total energy of possible tautomers is performed. The structure of the cyclic oxidation product of hydrazone 3-(1H-pyrrolyl-2)-[1,2,4]-triazolo(3,4-a)phthalazine existing in the crystal in the form of dimers linked by two hydrogen bonds is described.