INFLUENCE OF THE RATE OF IRON HEXATIANOFERRATE ON ITS SORPTION ABILITY IN RELATION TO SILVER, INDIUM AND GALLIUM CATIONS

The processing of phosphorites into elemental phosphorus is accom-panied by the formation of waste - cotrile "milk", in which indium, gallium, and silver are present. This waste can be considered as a cheap raw material for the production of rare and precious metals. In the scientific literature there are data on the sorption capacity of hexacyano-ferrates of iron, which has a crystal lattice with a channel diameter from 3.0 to 3.5Å. Investigation of the sorption process in the model system "Fe4[Fe(CN)6]3·10H2O - Ag+- In3+- Ga3+ - H2O" depending on the norm of iron hexacyanoferrate (sorbent). The initial concentration of silver, indium and gallium ions and their residual content in solutions were determined using the atomic absorption spectrophotometer "PerkinElmer Analyst 400" (USA). The microstructure of the initial iron hexacyanoferrate and iron hexacyano-ferrate, after sorption, was studied on the CarlZeissFESEM and JEOL brand "JXA-8230" (Japan). With a ratio to T:W equal to 1.75-2.5:100, the degree of sorption of Ag+ with iron hexacyanoferrate is 99.5 and 99.8 %. The highest degree of sorption (96.75%) of In3+ ions can be obtained with a sorbent weighing 3 g per 100 g of solution at 60oC. A high degree of sorption of Ga3+ cations is achieved at low (0.5:100 wt. h.) and high (3:100 wt. h.) consumption of iron hexacyanoferrate. It was revealed that iron hexacyanoferrate exhibits sorption properties simultaneously with respect to mono- and trivalent metals, and the basic laws of their sorption were established.

STUDY OF THE PROCESS OF OXIDATIVE DESULFURIZATION OF DIESEL FUEL IN THE PRESENCE OF CO-CATALYSTS

Continuous growth in consumption of oil in the world, as well as ever-increasing quality requirements stimulate the search for new scientific and technological solutions to directionally affect the characteristics of petroleum products, including their chemical composition. The advantages of oxidative desulfurization before hydrotreating are the absence of the need to use hydrogen, as well as small capital and energy costs, since the method does not require high temperatures and pressures. The purpose of this work was to study the oxidation process of diesel fuel and to search for the optimal mode of oxidative desulfurization of diesel fuel in the presence of transition metals salts with the addition of mineral acids. The object of the study is a straight-run diesel fraction of the Pavlodar Petrochemical Plant with boiling temperatures of 180-350°C. The oxidation process was carried out with hydrogen peroxide in the presence of salts of the transition metals molybdenum, vanadium and tungsten. The article defined the basic physico-chemical characteristics of straight-run and desulfurized diesel fractions. The optimal catalyst (Na2MoO4) was selected at a molar ratio of metal to sulfur of 1:100 for the oxidation process of straight-run diesel fractions. As a result of oxidative desulfurization of diesel fuel in the presence of sodium molybdenum perox complexes, the total sulfur content decreased by 42.9%, and with the addition of sulfuric acid by 56.5%. An increase in the cetane index from 56.3 to 58.6 was revealed in the presence of sodium molybdate with the addition of sulfuric acid.

DFT STUDIES OF STRUCTURAL PARAMETERS, VIBRATIONAL FREQUENCIES AND NMR SPECTRA OF 3-(1H-BENZO[D]IMIDAZOL-1-YL)-N'-(TOSYLOXY)PROPANIMIDAMIDE

Amidoxime derivatives have practically valuable biological properties. We have previously obtained new spiropyrazolinium compounds by arylsulfo-chlorination of β-aminopropioamidoximes, but in case of β-(benzimidazol-1-yl)pro-pioamidoxime we have obtained O-substitution product – 3-(1H-benzo[d]imidazol-1-yl)-N'-(tosyloxy)pro-panimidamide. The aim of the work is predicting of structural parameters (bond lengths, bond angles), vibrational frequencies and NMR spectra of 3-(1H-benzo-[d]imidazol-1-yl)-N'-(tosyloxy)propanimidamide. The calculations were performed using Gaussian 09 package. Structural parameters and vibrational frequencies was calculated using DFT (B3LYP/B3PW91/WB97XD)/6-31G(d,p). 1H and 13C NMR was predicted using DFT B3LYP/6-31G(d,p)-GIAO in DMSO. All calculated values are in good agreement with experimental data. The calculated bond lengths and bond angles were compared with results of X-ray structural analysis. The best correlation coefficient was 0.981 (calcu-lations with B3LYP level). For bond angles, the best result was obtained with B3LYP level (0.990). For vibrational frequencies correlation coefficients between the calculated and experimental values were 0.997 (B3LYP), 0.996 (B3PW91) and 0.995 (WB97XD). The most accurate method was used for predic-ting NMR spectrum. The correlation coefficients between the experimental and calculated 1H and 13C chemical shifts were 0.949 and 0.999 respectively.

IMPACT OF NEODYMIUM AND SCANDIUM IONIC RADII ON SORPTION DYNAMICS OF AMBERLITE IR120 AND AB-17-8 REMOTE INTERACTION

The aim of this research work is comparative study of influence of ionic radii of heavy metal ions of neodymium and scandium on their sorption process from corresponding water solutions of sulfates by sorbents such as individual ion-exchangers Amberlite IR120, AB-17-8 and mixture of these sorbents related to interpolymer system Amberlite IR120-AB-17-8 at the various molar relations. Laboratory experiments of this work of sorption heavy ions of neodymium and scandium were carried out and inves-tigated by using the following physico-chemical methods of analysis: conductometry-based on the electrical conductor, pH-metry-based on the concentration of hydrogen ions, colorimetry, atomic-emission spectro-scopy. Ion-exchangers in the interpolymer system undergo remote interaction with further transition into highly ionized state. There is formation of optimal conformation in structure of the initial ion- exchangers. Significant increase of ionization of the ion-exchange resins occurs at molar ratio Amberlite IR120:AB-17-8 = 5:1. Significant increase of sorption properties is observed at this ratio due to mutual activation of ion-exchangers. The extraction rate of Nd3+ ions in 48 hours is 42.32%, and the extraction rate of Sc3+ ions is 38.06%. A possible reason for higher sorption of neodymium ions in comparison with scandium ions is maximum conformity of globes of internode links of Amberlite IR120 and AB-17-8 after activation to sizes of neodymium sulfate in an aqueous medium.

STUDY OF BIOLOGICAL ACTIVITY OF RACEMIC AND OPTICALLY ACTIVE ESTERS OF NAPHTHENIC AND FATTY ACIDS BASED ON UNSATURATED OXYESTERS

Petrochemical products based on petroleum naphthenic acids have special properties. Esters of naphthenic acids possess practically valuable organic compounds. The aim of this work is the development of effective methods for the preparation of aromatic esters based on naphthenic and individual fatty acids which is a very promising direction in the medicine practice. The synthesis of unsaturated racemic and chiral oxyethers was carried out on the basis of the interaction of chloromethylpropargyl (allyl) esters with carbonyl compounds with the participation of metallic zinc. Also, to study the biological activity, racemic and optically active esters were synthesized based on naphthenic acids and unsaturated racemic and chiral oxyesters. As test cultures used: gram-positive (Staphylo-coccus aureus-Staphylococcus aureus), gram-negative (Pseudomonas aeruginosa – Pseu-domonas aeruginosa, Escherichia coli) bacteria, as well as yeast-like fungi of the genus Candida - Candida albicans. Analysis of the biological activity of the synthesized compounds showed that optically active bicyclo [2.2.1] hept-5-ene-2-methylol monoesters have higher antimicrobial and antifungal activity compared to their racemic analogs and drugs used in medicine.

CYCLODEXTRIN INCLUSION COMPLEXES OF PHARMACEUTICALLY ACTIVE DERIVATIVES OF THE CYTISINE ALKALOID AND THEIR HEMORHEOLOGICAL ACTIVITY

The alkaloid cytisine is of great importance for modern pharmacological studies. This alkaloid can be used as a component of the supramolecular system with cyclic oligosaccharides, namely β-cyclodextrins, which have a truncated cone-shaped molecule with internal protons Н3 and Н5 and external ones Н2 and Н4. The aim of the work is to obtain inclusion complexes of pharmaceutically active derivatives of the alkaloid cytisine. The inclusion complexes of cytisine alkaloid derivatives with β-CD and 2-HP-β-CD were obtained by the coprecipitation method. Thermogravimetric, differential thermal, and differential scanning calorimetric analyzes were performed. It was shown that inclusion complexes of substrate with cyclodextrin cavity of receptors were formed. The greatest change in the chemical shifts of protons during the formation of supra-molecular complexes occurs with the internal protons H-3 and H-5 of the cyclodextrin cavity. All calculated values are in good agreement with experimental data. The prepa-ration of supramolecular complexes has been proven using a variety of physicochemical methods of analysis. According to DSC data, the process of complexes destruction in the temperature range of 30-610°C was studied in comparison with the data of the initial cyclodextrin. The hemorheological effects of the investigated samples were studied in vitro. Among four samples studied, two samples showed the ability to reduce blood viscosity in vitro in the blood hyperviscosity model.

DIVARENT EQUILIBRIUM IN MULTI-COMPONENT SYSTEMS

The structure of the phase complex of the six-component reciprocal system Na, K, Mg, Ca || SO4, Cl-H2O at 500C in the region of crystallization of anhydrite (CaSO4) was studied by the translation method, and variants of the formation of divariant fields during the transition of the system from the five-component to the six-component state were shown

MODIFIED WITH VARIOUS ADDITIVES ARYLALYCLIC COPOLYIMIDES AND COMPOSITE FILMS BASED ON THEIR BASIS

lopment of arylalicyclic copolyimides based on alicyclic dianhydride, aromatic dianhydrides of benzophenone- and diphenyloxidetetracarboxylic acids with 4,4'-diaminodiphenyl oxide at various ratios of alicyclic and aromatic dianhydrides, as well as various compositions based on these copolymers with low- or other high-molecular compounds that enhance the characteristics of the polymer matrix. Composite films were formed from solutions of the obtained polymer mixtures, and their properties were studied. It was noted that at optimal ratio of components, the films have improved thermal and strength properties, etc., exceeding the analogous properties of the initial arylalicyclic copolymer, while the elasticity has acceptable values for such material. The best characteristics had the composite films formed from a ternary composition of copo-lyimide-polyethylene glycol-alkylated montmorillonite. Metal-containing composite films, along with higher thermal stability compared to unmodified copolyimide, were resistant to aggressive reagents, lower values of specific volume and surface resistance, higher viscosity values, and different colors depending on the nature of the salt. By introducing a silicon-containing compound into the copolyimide solution, the new polymer systems have been obtained, and the porous films could be formed.

NEW PHARMACOLOGICALLY ACTIVE COMPOUNDS BASED ON 5-HYDROXY-7-METHOXY-2-PHENYLCHROMAN-4-ONE

The reaction of 5-hydroxy-7-methoxy-2-phenylchroman-4-one with dibromoalkanes in acetone in the presence of potassium carbonate proceeds according to the Michael’s retro-reaction O-alkylation and leads to the formation of the corresponding 2-(bromo-alkoxy) chalcones. The structure of the synthesized compounds was confirmed by IR-, 1H- and 13C-NMR spectroscopy. The cytotoxic, hepatoprotective and anti-inflammatory effects of chalcone derivatives (2-3) were studied for the first time in vitro and in vivo.

SPECIAL FEATURES OF COPPER AND NICKEL SORPTION ON LOW-BASE ANIONITES

In the work, the regularities of the process of sorption of copper and nickel ions from model solutions by low-base anionites containing coordination secondary groups are investigated. The main kinetic and concentration coordination characteristics of the process of complexation of copper and nickel ions with ligand groups of a low-base sorbent are determined.Potentiometric titration shows that anionite contains low-base functional groups, the pK of which is equal to 7.2.It is established that the process of sorption of copper ions by low-base macroporous anionite is characterized by a high initial rate and rapid achievement of equilibrium, which ensures absorption of copper ions about 70% of the equilibrium values in the first 10- 15 minutes.The main parameters of the sorption process are determined. Analytical description of sorption isotherm in coordinates of Langmuir equation is carried out. It was shown that due to high rates, the degree of extraction from solutions with a concentration of 10- 15 mmol/l under equilibrium conditions reaches 99.6-98.3%.Studies of the sorption process in a dynamic mode showed the possibility of separating heavy metal ions from aqueous solutions on new low-base anionites.