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

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Vol 56, No 3 (2020)
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https://doi.org/10.29235/1561-8331-2020-56-3

PHYSICAL CHEMISTRY

263-270 613
Abstract

Using non-empirical quantum-chemical calculations (with the density functional theory of DFT/B3LY-P/6-31G(3d,p) level) the geometric characteristics of sorption complexes of sulfur dioxide with primary, secondary and ternary amino groups of anion exchangers, synthesized by amination of nitrile groups of polyacrylonitrile fiber with the ethylenediamine or dimethylaminopropylamine, were calculated and their structures are visualized. The main regularities of SO2 sorption from air and features of the ongoing interactions in the polymer phase are established: 1) SO2 with primary and secondary amino groups of anion exchanger mainly interacts with the water molecules and practically does not form direct bonds with the nitrogen of the functional groups; the introduction of an oxygen molecule does not change the state of the system; 2) in the phase of anion exchanger with ternary amino groups, SO2, interacting with water molecules, spontaneously transforms into a hydrosulfite ions with proton transfer to ternary nitrogen; in the presence of an oxygen molecule in the system, barrier-free formation of the peroxy acid anion (SO3OO2-) occurs with the possible further oxidation of hydrosulfite to hydrosulfate.

COLLOIDAL CHEMISTRY

271-277 545
Abstract

It is shown that the stability of the water and salt dispersion of kaolin decreases with the introduction of a cationic polyelectrolyte and its mixtures with a surfactant. The flocculating ability of the cationic polyelectrolyte decreases with increasing content of ionic groups. An increase in flocculation in a salt medium was established with the introduction of the mixture of polyelectrolyte with an anionic surfactant, as well as with the sequential addition of components to the kaolin dispersion.

278-283 816
Abstract

The surface activity of amphiphilic polymers increases with an increase in the content of hydrophobic groups in the polymer and in the presence of low molecular weight surfactants. Binary systems containing methacrylic acid copolymer with а-pinene and cetyltrimethylammonium bromide show that the toluene solubilization increases by 1,4 times compared to a polymer without surfactant and by 1,3 times when the surfactant concentration in the solution is below the critical micelle concentration.

ANALYTICAL CHEMISTRY

284-292 747
Abstract

Extraction of six acid type penicillins (penicillin G, penicillin V, oxacillin, cloxacillin, nafcillin, dicloxacillin) from their water solutions by polar organic solvents (n-hexane, toluene, chloroform, isoamyl alcohol) was studied. Penicillins were quantified by high performance liquid chromatography-mass spectrometry. The penicillins distribution constants were calculated. А possibility of developing a fast, effective and inexpensive method for the determination of trace amounts of acid type penicillins in foodstuffs using extraction by chloroform was shown.

ORGANIC CHEMISTRY

293-300 570
Abstract

The method for maleopimaric acid aminoamides synthesis has been developed, which involves the treatment of maleopimaric acid with an excess of thionyl chloride at 18-20 °С and the subsequent reaction of the obtained maleopimaric acid chloride and aromatic diamines (1,4-diaminobenzene, 4,4’-diaminodiphenyl) in 80.5-94.3 % yields. The reaction of maleopimaric acid aminoamides with aliphatic and aromatic aldehydes (isovalerianic aldehyde, benzaldehyde, 4-methoxy-benzaldehyde, 4-chlorobenzaldehyde) gave maleopimaric acid azomethines containing mesogenic groups (4-biphenyl, 4-phe-nylaminobezilidene) in 56.5-99.3 % yields. Maleopimaric and citraconopimaric acid 4-biphenylamides were first synthesized by the reaction of acid chlorides of these acids and 4-aminobiphenyl in yields of 91.3-94.8 %. It was established that the obtained substances are optically active and the specific rotation ([α]D) of the synthesized compounds is -45.0° ÷ -118.2°. It has been shown that the chiral LC phase is formed once the obtained additives (amides and azomethines of maleopimaric acid) are introduced into the nematic liquid crystal matrix (MLC 6809-000, Merck). The helical twisting power of the studied compounds reaches 12.4 pm-1. The data obtained can be applied in the development of new industrial chiral LC compositions for use in the electronic and LC industry, e.g. TN LCD fabrication.

301-310 1291
Abstract

Nicotinic (3-pyridinecarboxylic) acid is one of the most important vitamins as well as substance with versatile physiological activity, since it plays significant role in the human organism. Nicotinic acid (niacin, vitamin PP, vitamin B3) is widely used in medicine as drug which has a vasodilating effect, prevents the accumulation of cholesterol and normalizes the heart function. Isonicotinic (4-pyridinecarboxylic) acid is used for the production of valuable anti-tuberculosis drugs, antidepressants, etc. However, nicotinic and isonicotinic acids have various side effects: skin hyperemia, pruritus, formation of stomach peptic ulcers, liver dysfunction and hyperglycemia. To reduce the severity of side effects, their slightly soluble salts, esters or amides are obtained. The synthesis of nicotinic and isonicotinic acid esters with vanillin benzaldehydes, cholesterol, 8-hydroxyquinoline, quinine and (4,5-dichloroisothiazol-3-yl)methanol is described. Esters were obtained by acylation of hydroxybenzaldehydes and alcohols with nicotinic and isonicotinic acid hydrochlorides in the presence of triethylamine in anhydrous methylene chloride. The IR- UV- and NMR spectra of the compounds obtained are presented.

311-317 522
Abstract

3-benzyl-6-isobutylpiperazin-2,5-dione [cyclo(leucylphenylalanyl)], 3-isobutylpiperazin-2,5-dione [cyclo(-leucylglycyl)] and 3-(sec-butyl-)-6-isobutyl-piperazine-2,5-dione [cyclo(leucylisoleucine)] have been obtained by cyclization of methyl esters of tert-butyloxycarbonyl derivatives of dipeptides, for the synthesis of which both carbodiimide-promoted peptide bond formation and the mixed anhydride method were used.

BIOORGANIC CHEMISTRY

318-332 818
Abstract

Two test-systems for a direct and an indirect enzyme-linked immunosorbent assay (ELISA) of peptide antibiotic bacitracin (BC) were developed and studied. For the both systems, polyclonal antibodies were obtained by immunizing rabbits with a conjugate of BC with keyhole limpet hemocyanine synthesized using reaction between the peptide and the high molecular weight protein in the presence of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC). The product of BC linking to thyroglobulin which was activated with EDC and N-hydroxysulfosuccinimide served as conjugated antigen on a solid phase in the indirect ELISA. For the direct ELISA, the antibodies against BC were immunochemically immobilized onto microplate surface, while the liquid phase contained a conjugate of BC with horseradish peroxidase. This conjugate was obtained by successive reactions of antibiotic amino groups coupling to periodate oxidized carbohydrate chains of enzyme and the reducting of formed Shiff’s base with sodium borohydride. Conjugated antigens binding to anti-BC antibodies provided maximum colorimetric signals of 2.0 and 1.2 optical units for the direct and indirect ELISA, respectively, and depended on BC content in the liquid phase. Antibiotic concentration that caused the inhibition of binding by 50 % was 2.6 ng/ml in the direct ELISA and 10.0 ng/ml in the indirect ELISA. The simple and sensitive direct ELISA system was used as a prototype of the finished reagent kit and a method for measurements with technical-analytical parameters and metrological characteristics allowing the determination of BC residues in a variety of foods including 14 items in a concentration range of 9.0 to 405.0 pg/kg with proper accuracy and precision.

333-338 860
Abstract

Biospecific sorbents for the removal of IgG and subclasses from biological fluids based on oligopeptides that contain aromatic protein residues have been created. A functional assessment of high-quality experimental samples of sorbents and their preferences for IgG subclasses was carried out. It was found that each sorbent has good characteristics for removing IgG from biological fluids, but the sorbent based on Phe-Trp-DTyr is more effective in binding of total IgG. With respect to IgG subclasses, the best binding results are as follows: Phe-Gln-Tyr-OMe - IgG1 (86,53%), Phe-Ala-Tyr - IgG2 (60,2%), Phe-Trp-DTyr - IgG3 (59,52%) and IgG4 (55,05%).

POLYMER CHEMISTRY

339-351 996
Abstract

Swelling of acrylamide and sodium acrylate copolymer polyelectrolyte hydrogel in aqueous Cu(II) chloride solutions with additives of proteinogenic amino acids glycine and L-histidine has been studied. Research relevance is due to the application of such systems in agrochemical products that are supposed to have high water absorption capacity in the presence of microelements ions and amino acids, which are used to prevent nutritional deficiency and make plants resistant to adverse weather conditions and diseases. Gravimetry, atomic absorption spectrometry, FTIR ATR spectroscopy and molecular absorption spectrophotometry were used. The impact of acidity (pH 3, 5 and 7) of aqueous Cu(II) chloride solutions with amino acids additives on the hydrogel swelling degree and Cu(II) ions absorption has been determined. The reasons for changes in the hydrogel swelling degree in aqueous Cu(II) chloride solutions in presence of glycine and L-histidine have been found. The main product of the crosslinked copolymer interaction with the components of 0.01 M aqueous Cu(II) chloride solution with the addition of 0.04 M glycine or L-histidine at pH 3 has been assumed to be a mixed Cu(II) ions complex with functional groups of both copolymer and amino acids.

GEOCHEMISTRY

352-364 515
Abstract

Effect of soil temperature on concentration and total reserve of cadmium, lead and uranium in the interstitial (pore) water of waterlogged sod-podzolic medium loamy soil after their keeping at the definite temperature in the range of 15-40 °C was established. It was found that in the water-saturated soil samples, portions of the cadmium, lead and uranium in the soil pore solution were correlated as follows: αCd (0.2-0.3%) >> αPb (0.08-0.10 %) ≥ αU (0.03-0.08%). An increase in temperature leads to a change in the physicochemical state of HM in the soil and, consequently, to a change in their content in soil pore moisture, where elements are concentrated in the most mobile and biologically accessible migration-active forms. The character and extent, to which temperature affects the concentration and total reserve of heavy metal (HM) in the soil water, depended on the chemical nature of HM and peculiarities of soil. The 5 °C temperature increase in the range of 15-40 °C caused the content of Pb in the soil pore water to increase an average of 4.5 %, and Cd and U to decrease by 4.4 and 13 %, respectively. The iron content in the soil water increased with increasing temperature, which indicated a decrease in the sorption capacity of iron hydroxides of soil, which probably significantly affected the fixation of Pb in the soil. In accordance with the values of the distribution coefficients of HM in the “solid phase-soil pore solution” system, the fixation of HM in the soil increased in the following way: Cd (180-230) << Pb (480-590) ≤ U (570-1620). The degree of Pb fixation in the soil increased with increase in the temperature of the soil, and Cd and U - with its decrease. Weakening of the HM fixation in the soil leads to an increase in their mobility and bioavailability and worsens the ecological state of terrestrial ecosystems.

TECHNICAL CHEMISTRY AND CHEMICAL ENGINEERING

365-373 543
Abstract

Processing of potash production slime storage lyes with the aim to obtain useful components with evaporation method was investigated. It was estimated that during the first and the second stages of evaporation in vacuum crystallization devise (VCD) sodium chloride was crystallized from the hot (90-95 °C) lye, and potassium chloride - when cooling down to 35 °C. Content of basic components (KCl & NaCl) in the precipitate was more than 90 %. During the third stage, while cooling down to 20-25 °C, and the fourth stage from the hot (90-95 °C) lye, a mixture of sodium and potassium chlorides was crystallized. During the next evaporation and cooling up to 20-25 °C together with sodium and potassium chlorides, carnallite was obtained, the decomposition of which leads to potassium chloride formation.

374-384 609
Abstract

The development of a technology for the regeneration of used asphalt concrete coatings is presented, provided that industrial wastes are used and environmentally friendly asphalt concrete coatings are obtained. For research, the technology of dispersing and mixing the waste was chosen to achieve its homogeneity and activation of the mixture in order to increase the physicochemical interaction with binders. It was shown that heavy metals contained in waste and in asphalt granulate are reliably blocked in materials based on organohydraulic binders (OHB), their migration to the environment is significantly reduced. With the optimum content of bitumen emulsion and cement, the effect of maximum structural strength of the road building material and maximum fixation of heavy metal ions is observed. The proposed technical solutions are supported with theoretical calculations and allow environmental-friendly regeneration of asphalt concrete pavements.



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