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Proceedings of the National Academy of Sciences of Belarus, Chemical Series

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Vol 54, No 2 (2018)
View or download the full issue PDF (Russian)
https://doi.org/10.29235/1561-8331-2018-54-2

PHYSICAL CHEMISTRY 

135-145 607
Abstract
Nanocapsules consisted of magnetic core and polyelectrolyte shell on the basis of chitosan or its polyethylene glycol (PEG) grafted copolymers (CH) and polystyrene sulfonate (PSS) were obtained by layer-by-layer assembly. The influence of the number of CH/PSS bilayers in a shell, polymerization degree of CH, and the presence of grafted PEG chains on aggregative and sedimentation stability of the obtained nanocapsules in different media (water, 0.9 % NaCl solution, fetal bovine serum (FBS)) was discussed. It was shown that the diameter of PSS-terminated (CH/PSS)n nanocapsules in FBS does not change at 37 °С for 6–8 h. Adsorption of bovine serum albumin on the surface of the layer-by-layer nanocapsules stabilizes them in isotonic 0.9 % solution of NaCl and FBS. Co-introduction of copolymer and albumin in the shells improves generally the aggregative stability of nanocapsules in water and allows one to obtain stable nanocapsules with magnetic core for fewer adsorption cycles.
146-153 646
Abstract

The properties of oxide gas sensitive compositions In2O3–Ga2O3–WO3 prepared by sol-gel method, with tungsten oxide 5 % wt., gallium oxide 4 % wt., have been investigated. Tungsten oxide addition was established to lead to significant increase in nitrogen dioxide sensitivity. The composition structural features were studied by X-ray diffraction analysis and Raman spectroscopy. It was found that thermal treatment of mixed sols In2O3, Ga2O3, WO3 leads to the formation of hete- rogeneous two-phase material containing (In, Ga)2O3 solid solution and monoclinic WO3 phases. According to X-ray diffraction data, the growth in size of WO3 and In2O3 grains during heat treatment in the mixed In2O3–WO3 composition decelerates
as compared to individual oxides. It is assumed that significant increase in the sensitivity to low concentrations of nitrogen dioxide of the composition containing WO3 additive, as compared to the initial one, may be due to the presence of multiply charged adsorption centers (W4+, W5+, W6+), as well as due to the complication (according to EPR) of the defect structure
of the double In2O3–WO3 and a triple In2O3–Ga2O3–WO3 composition as compared to the initial oxides. Single-electrode semiconductor nitrogen dioxide sensors with a low threshold of detection (<< 1 ppm) and low power consumption are fabrica- ted. The response of gas sensors based on the In2O3–Ga2O3 (4 % wt.)–WO3 (5 % wt.) composition to gas mixtures containing 10 ppm of NO2 in air has a pronounced maximum at powers of 80–90 mW.

INORGANIC CHEMISTRY 

154-160 749
Abstract

The Bi4Ti3–2xNbxCoxO12 (x = 0.05, 0.10, 0.15) solid solutions have been synthesized using ceramic method, their crystal structure, thermal expansion, electrical and dielectric properties have been studied. It has been established that Bi4Ti3–2xNbxCoxO12 titanates are p-type semiconductors whose electrical conductivity at low temperatures is higher, but
at high temperatures is lower than for the base Bi4Ti3O12 bismuth titanate. It has been found that partial co-substitution of titanium by niobium and cobalt in Bi4Ti3O12 leads to the increase in the size of the unit cell of the Bi4Ti3–2xNbxCoxO12 solid solutions, a decrease in their Curie temperature, a decrease in the dielectric constant and dielectric losses, and slightly affects the magnitude of their linear thermal expansion coefficient. For Bi4Ti3.8Nb0.1Co0.1O12 and Bi4Ti3.7Nb0.15Co0.15O12 solid solutions, a sharp increase in the activation energy of electrical conductivity has been observed at the transition from the ferroelectric region to the paraelectric region.

ANALYTICAL CHEMISTRY 

161-167 815
Abstract

Extraction systems consisting of n-heptane and 1-methylphenanthrolinium benzenesulfonate methanol solution have been investigated. Distribution constants in systems n-heptane – polar phase for aromatic hydrocarbons and the increments of methylene group have been calculated. It has been found that the polar phase is highly structured and has a large increment of the methylene group. It has been also found that solutions of 1-methylphenanthrolinium benzenesulfonate
in methanol possess high affinity for condensed aromatic hydrocarbons, which value exceeds all the previously studied extraction systems. Extraction of hydrocarbons with isolated aromatic systems by 1-methylphenanthrolinium benzenesulfonate methanol solution is negligible. The systems studied can separate condenced polyaromatic hydrocarbons from hydrocarbons with isolated aromatic systems. The effect found may be used for preparing modified state phases in liquid chromatography.

ORGANIC CHEMISTRY 

168-179 601
Abstract
4-Aminoacetophenone oxime is convenient and accessible reagent for chemical modification of substituted aromatic aldehydes to produce ligands for complexation with transition metals. By the reaction of 4-aminoacetophenone oxime with aldehydes vanillyl series by boiling in absolute methanol in the presence of catalytic amounts of glacial acetic acid, (E,E)-azomethyneoximes with 70–85 % yields were synthesized. By the reaction of 4-aminoacetophenone oxime with 9-phenanthrene carboxaldehyde, ferrocene carboxaldehyde, 5-phenylisoxazole-3-carboxaldehyde and 5-(p-tolyl)isoxazole- 3-carboxaldehyde, corresponding (E,E)-azomethineoximes with 77–84 % yield were obtained. By acylation of the (E)-1-{4-(E)-benzo[d][1,3]dioxol-5-ylmethyleneaminophenyl}ethan-1-one oxime in a solution of dry diethyl ester in the presence of triethylamine, corresponding ester was synthesized with 84 % yield. By quantum chemical calculations using DFT method using level B3LYP1 / MIDI using the theory GAMESS software package and a MIDI basic set, we defined the most thermodynamically stable isomers of the synthesized compounds. In the process of calculations a full optimization of all geometric parameters to achieve a minimum total energy (E,E)-, (E,Z)-, (Z,E)- and (Z,Z)-azomethineoximes was carried out.

BIOORGANIC CHEMISTRY 

180-189 690
Abstract
A reagent kit EIA-FUMONISIN for the determination of mycotoxins of fumonisin B group in feeds and foods by a direct competitive enzyme immunoassay using microtitration plate has been developed and tested. The evaluated technicoanalytical parameters of the kit and metrological characteristics of the technique of measurements correspond to the mo- dern level of immunoassay development and provide the determination of fumonisin group B content of agricultural products in a range of 0.11 to 6.0 mg/kg with proper accuracy and precision.
190-196 776
Abstract
In order to determine the optimal redox partners of CYP124 M. tuberculosis in reconstituted in vitro system we carried out heterologous expression, isolation and purification of recombinant CYP124 Mycobacterium tuberculosis and candidate redox partners: Fdx, FdR, FprA, Adx, AdR, CPR, Arh1_A18G, Etpfd. CYP124 was shown to exhibit the highest catalytic activity in system with S. pombe mitochondrial electron transfer proteins: Etp1fd и Arh1_A18G.
197-203 807
Abstract

Polyethyleneglycol (PEG) is nontoxic, nonimmunogenic, hydrophilic, chargeless and nonbiodegradable poliymer. Its usage as a part of therapeutics protein drugs is common in medicine practice. It is known that covalent attachment of PEG conduces to prolong blood circulation half-lives, improves drug solubility and stability and reduces immunogenicity. It allows optimizing pharmacodynamic and pharmacokinetic drug properties. The goal of structure optimization
of therapeutic proteins conjugates with PEG is to reduce loss of biological activity. It can be reached through controlled site- specific pegylation. We introduce two-step modification of proteins with branched polyethylenglycols via click-chemistry, synthesis of branched PEG azide reagent on the base of tris(hydroxymethyl)aminomethane with three linear PEG polymers. At first, we introduce alkyne groups with NHS-ester of alkyne acid in BSA protein. Then, branched PEG azide reagent reacts with alkyne function via CuAAC. Purification of the conjugates was done via gel-chromotography. Number of modifications was calculated from MALDI mass-spectra.

POLYMER CHEMISTRY 

204-215 1024
Abstract
The process of cellulose modification with a mixture of orthophosphoric acid and ammonium polyphosphate or pentasodium triphosphate in a carbamide medium or with the same compounds in presence of magnesium salt was studied. Under these modification conditions, the esterifying composition undergoes direct anionic reorganization with the formation of linear short-chain polyphosphates. It has been established that the level of fire protection of modified cellulose using phosphate formulations depends both on the phosphorus content in the fabric and on the composition of the ester groups introduced. The effectiveness of fire resistance of the obtained materials increases with the length of the phosphate chains. It is shown that in the process of cellulose modifications using impregnated compositions in the range of 130–160 °C cellulose phosphates with small losses in strength of cotton materials (no more than 10–15 %) are produced. The resulting cellulose phosphates have a fire resistance level corresponding to difficult-burning materials.

GEOCHEMISTRY 

216-225 636
Abstract

Technical mixtures based on PCBs (Sovol plasticizer) were used for the more than 30 years for paint and varnish manufacture in Lida city (Grodno region, Belarus). Soils on the territory of enterprises and adjacent area have been contaminated as a result of Sovol leakages as well as releases of waste water and solid waste. Investigations of PCBs content in soil have been fulfilled in the period from 2004 to 2014. PCB congeners (PCB-28, PCB-52, PCB-101, PCB-118, PCB-153, PCB-138 and PCB-180) in soil samples were detected by gas chromatography with ECD and chromatography mass spectrometry. Since the start of investigation, PCBs content in soil has been decreased with the rate of about 2 mg / kg, or 9 %, per year. Despite the almost 20-year period after Sovol was banned, the industrial area is still contaminated and the residual concentrations of PCBs are higher in dozens and hundreds times than maximum permissible level. The similarity of the PCB congeners profiles in the soils of the industrial site and the adjacent area, especially in the runoff area, indicates the redistribution of PCBs with runoff and the formation of secondary pollution site.

226-230 506
Abstract
Geochemical features of the rocks of the Rusinovsky complex of the crystalline basement of Belarus are revealed. The rocks are characterized by normal alkalinity, high magnesia, low and medium alumina content, low iron content, except for diabases. In the trace element composition of rocks depletion with LILE elements (Sr, Ba, Zr, Nb) and increased content of Cr, Ni and C were observed. Two petrochemical series are distinguished in the rocks: magnesian (gabbroids) and titanium-ferruginous (diabase).

TECHNICAL CHEMISTRY AND CHEMICAL ENGINEERING 

231-237 1120
Abstract

The carnallite decomposition by water to obtain potassium chloride was studied. Optimal parameters of this process (temperature, time, S:L ratio, ore crushing degree) are determined. It is shown that the optimal ratio of solid to liquid is 2:1.1 for the full carnallite decomposition. The maximum degree of carnallite decomposition and KCl recovery are achieved at a reaction time of 30 minutes. It is shown that for water decomposition of ore with a high content of carnallite (without
insoluble impurities), too fine ore crushing is not required. The main requirement for crushing is the release of the mineral. It is possible to increase KCl content to 95 % and the degree of carnallite decomposition to 99.0–99.5 % by the use of the precipitate washing.

238-244 663
Abstract

The most promising region of glass compositions for obtaining hollow glass microspheres was determined using literature analysis. The main physical and technical characteristics of glasses have been studied and the dependence of the glasses properties on composition has been established. The influence of rheological properties of glasses near liquidus temperature on the processes of separation of gases previously dissolved in glass was established. It was shown that the loss
of the glass mass upon reheating is much higher than the amount of sodium sulfate dissolved in the melt and may be due to incomplete decomposition during melting of carbonates (in particular, sodium carbonate) included in the charge composition, as well as volatilization of B2O3.

245-249 561
Abstract
Methods of determining the individual concentrations of Na-CMC and PAA in their joint solution are studied. Modified Kjeldahl method to determine the concentration of PAA is proposed. Strong correlation of the refractive index and the concentration of Na-CMC is found. Weight method to determine common concentration is examined experimentally.

SCIENTISTS OF BELARUS 



ISSN 1561-8331 (Print)
ISSN 2524-2342 (Online)