Voprosy khimii i khimicheskoi tekhnologii (Issues of Chemistry and Chemical Technology)

7-12

Authors: O.Yu. Voskoboynik

The effective and convenient methods for preparation of 6-(heterocyclyl-N-ylmethyl)-3-R1-9-R2-2H-[1,2,4]triazino[2,3-c]quinazolin-2-ones via the interaction of secondary cyclic amines with 6-(chloromethyl)-3-R1-9-R2-2H-[1,2,4]triazino[2,3-c]quinazolin-2-ones are described in the paper. The synthesis of the intermediate mentioned above has some features associated with the alternative possibility of the formation of 3-R1-10-R2-benzo[f][1,2,4]triazino[2,3-d][1,4]diazepine-2,7(6H,8H)-diones. The individuality of the synthesized compounds has been proved by liquid chromatography-mass spectrometry; their structure has been confirmed by 1Н NMR, 13С NMR and mass spectrometry. The characteristic signals in 1Н NMR and 13С NMR spectra are determined. The features of molecule fragmentation under the electron impact are elucidated. Some of the obtained compounds are evaluated for anticancer action according to National Cancer Institute (USA) protocol. The presence of fluorine or azepan fragment in the molecule of the compounds under study appreciably improves both the intensity and the spectrum of the cytotoxic action. The most intensive inhibition of the cancerous cells enlargement is observed for the lines of non-small cell lung cancer, renal cancer, breast cancer and leukemia. The findings support the perspectives of the further investigations aimed to searching novel anticancer agents among the compounds under consideration.

19-26

Authors: N.Ya. Kuzmenko, S.N. Kuzmenko, O.V. Skrynnik

The reactions of the transeterification of tetrabutoxy titanium and poly(butoxy)titanoxanes by stearic acid at their varied mole ratios have been described. The structure of the synthesized compounds contains both reactive butoxy groups and fatty aliphatic units of stearic acid. These compounds are light-yellow or light-brown viscous liquids or solid substances (at room-temperature) which are very soluble in aliphatic, aromatic and chlorinated hydrocarbons. Their structures have been verified by elemental analysis, molecular mass measurement, infrared and 1H NMR spectroscopies. It has been shown that a part of resultant butanol reacts with stearic acid forming respective ester. The release of water in such a reaction leads to the condensation reactions with the formation of titanoxanes bonds in end products. It has been found that an increase in the tetrabutoxy titanium:stearic acid ratio in the course of transeterification up to 1:2 mole/mole does not result in a full substitution of butoxy groups near titanium atom with acyl group of stearic acid. The results of IR-spectroscopy of the end products suggested that the bonds between titanium atom and acyl group of stearic acid have a salt character.

29-33

Authors: O.S. Panteleieva, Ch.P. Akritidou, V.V. Boynik, V.I. Tkach

The article describes the results of the research on the quantitative determination of the sum of alkaloids in dry extracts of lupin seeds and roots by means of amperometric titration using heteropolyanions (HPA) of Keggin structure as an analytical reagent. As Keggin heteropolyanions have particular properties (i.e. constant composition, ion-exchangeable capability and redox power), they can form stable ion-associates with organic nitrogen containing cations which are readily soluble in organic solvents and characterized by a very low solubility in water. The interaction between organic cations of alkaloid sum (ƩAlc1+) and heteropolyanion РМо12О403– of 12-molybdophosphatic heteropoly acid (3ƩAlc1++PMo12O403–  (ƩAlc)3PMo12O40) is investigated. To determine the composition of ion-associates formed, the ratio of reactants is specified using amperometric titration with endpoint indication according to the strength of the diffusion current of Keggin PMo12O403– electroreduction. The results testify that the organic cations of alkaloid content in extracts of lupin seeds and roots interact with the heteropolyanion of 12-molybdophosphatic heteropoly acid in the molecular ratio ƩAlk1+:PMo12O403– = 3:1 and the reaction under study (ƩAlk1+ +PMo12O403– → (ƩAlk)3PMo12O40↓) proceeds stoichiometrically in aqueous solution in the range of рН 4.4 to 5.7 for the extracts of lupin seeds and of рН 5.2 for the extracts of lupine roots, correspondingly, with the formation of stable and marginally soluble ion-associates. The developed methods of the quantitative determination of alkaloids sum in dry extracts of lupine seeds and roots by means of amperometric titration using 12-molybdophosphatic heteropoly acid as an analytical reagent are notable for their simplicity, speed and sufficient sensitivity.

38-43

Authors: D.S. Androshchuk, N.D. Sakhnenko, M.V. Ved’, T.P. Yaroshok

The deposition of mixed oxides containing manganese with a high catalytic activity directly on the surface of the piston has been proposed in order to ensure the deep oxidation of fuel and conversion of CO into CO2 in internal combustion engines. Such a metal-oxides system can be formed in an alkaline-manganate electrolyte by the plasma electrolytic oxidation of the surface of aluminum casting alloys (AL25) which are used for the manufacture of piston diesel engines. The analysis of anodic polarization dependences in the solutions with a varied composition allowed determining the efficient operational electrolyte composition and optimal electrolysis parameters. The effects of oxidation parameters and processing time on the surface morphology, and manganese oxides content and composition in the coatings have been studied. An increase in the current density was shown to contribute to increasing the manganese oxides content in the coating and surface developing which provides a high catalytic activity in the oxidation of carbon (II) oxide.

48-54

Authors: O.M. Grytsenko, O.V. Suberlyak, Kh.Ya. Gishchak

The metal-containing co-polymers on the basis of quick-setting compositions of polyvinylpirrolidone with 2-hydroxyethyl-methacrylate are synthesized at room temperature in the presence of oxygen by polymerization under the presence of metallic dispersed fillers of different nature. It is determined that metals with negative electrochemical potential are polymerization catalysts. The activating effect grows with an increase in the metal electrochemical potential. The interrelation between cross-linking degree, chemical structure of obtained cross-linked co-polymers and reactive composition formula and metal nature is investigated. PVP grafting efficiency and PVP content in the co-polymer increase with an increase in the metal activity in polymerization initiation. It is proved that when the activity of metal is the highest the polymer with a minimum cross-linking degree is forming. The rising of polyvinylpirrolidone content in co-polymer results in an increase in the co-polymer hydrophily that provides sorption characteristics of metal-containing co-polymers. The interrelation between physical and mechanical properties and structure of obtained materials is determined; the possibility of their controlled synthesis with required cross-linking degree and set of properties is shown. The centrifugal molding method is proposed which allows obtaining quality film materials on the basis of synthesized metal-containing hydrogels with given thickness. Hydrogel film materials obtained by centrifugal molding have a high surface quality.

62-67

Authors: T.L Malysheva, A.L. Tolstov

In this work, we study the effects of the chemical reactivity and content of isocyanate groups in the macrodiisocyanate (MDI) or in the blends of MDI with polyisocyanate in an organic phase on the interfacial interactions, sorption and mechanical properties of organic-inorganic composites based on sodium silicate. To synthesize the MDI with the NCO groups content from 3.6 to 11.8%, the poly(propylene glycol) with relative molecular mass of 1000 or 2000 and the mixture of 2,4- and 2,6-isomers of tolylenediisocyanate are used. An increase in the content of the most reactive NCO groups of tolylene-2,4-diisocyanate in organic phase is stated to improve surface covalent interactions. FTIR-spectroscopy confirms the reaction between isocyanate groups of organic phase and silanol groups of inorganic phase. The intensification of the surface interactions and formation of hydrophobic urethane-silicate layer results in a decrease in water sorption ability and an enhancement of the mechanical properties of the composites obtained using both sodium silicate modified by polyacrylic acid and unmodified one.

72-77

Authors: O.V. Savvova, G.N. Shadrina

In this paper, we study the relationship between viscosity and structure formation of calcium silicophosphate glasses during heat treatment, this correlation being crucial in the development of bioactive high-strength glasses and coatings based on them. The features of the crystallization of segregating calcium silicophosphate glasses in the course of crystallization process have been reviewed. There is an increase in the number of the composition fluctuations of the glasses with a content of R2O = 20% (mas.) compared to the glasses containing 10% (mas.) R2O. An increase in the glasses viscosity in the temperature range of Tg to Tf is associated with the formation of the composition fluctuations and nucleators which act as nucleating agents for calcium phosphates. According to our findings, the metastable segregation at the initial stages of nucleation in glasses in a high viscosity range of 107 to 108 Pas promotes obtaining glass-ceramic coatings with fine volume crystallization; this feature is an essential condition for high mechanical properties of the final product. The data obtained can be used for the development of bioactive glasses and coatings on titanium to fill bone defects at the loaded areas, particularly in oral and maxillofacial surgery and hip replacement.