The dissociation constant of thiamine hydrochloride in an aqueous solution at 298.15 K and ionic strengths of 0.5, 1.0, and 1.5 (using potassium nitrate as the background electrolyte) is determined via potentiometric titration. The heat effects of the dissolution of crystalline thiamine hydrochloride in water and solutions of potassium hydroxide at 298.15 K and different ionic strengths of solution are measured, and the standard thermodynamic characteristics of dissociation are obtained on a variable-temperature calorimeter with an isothermal shell. The absorption spectra of aqueous solutions of thiamine hydrochloride in the pH range of 2.8 to 11.4 at 298.15 K are studied using spectrophotometric measurements. Vitamin B1 in aqueous solutions is found to behave like a monobasic acid. The thermodynamic characteristics of the dissociation of thiamine hydrochloride in an aqueous solution are determined under standard conditions.

A number of phthalonitriles with regularly varying peripheral phenoxyl substituents have been obtained by nucleophilic substitution of the nitro group/bromine atom with fragments of phenol derivatives. Based on these phthalonitriles, magnesium complex of with phthalocyanine ligands of various structures have been synthesized. For such complexes, the role of the nature, location, and number of substituents has been determined when considering the spectral and fluorescent parameters in various solvents. It is shown that, for the metal phthalocyanines under study, the spectral characteristics are largely influenced by the location of the substituent, while the values of the fluorescence quantum yields are influenced by all of the above characteristics.

Synthesis of 5-phenyl-2,3,7,8,12,18-hexamethyl-13,17-diethylporphyrin and its dinitro derivatives, containing nitro groups in positions 10, 20 of the porphyrin nucleus, was performed. Structure of the obtained compounds was proved by NMR, IR, mass spectroscopy, and EAS spectra. The kinetics of formation reactions of zinc, copper, and cobalt complexes of the synthesized porphyrins in pyridine and acetic acid was investigated. Connection of the porphyrin ligands reactivity with electronic effects of nitro groups, effects of the spatial distortions of the porphyrin nucleus, and the structure of solvation shells of 3d-metal salts is discussed.

The difficulty of the discharge of nickel ions due to the adsorption of the addition of diaminomeleodinitrile on the electrode surface contributes to the formation of a fine crystalline precipitate with high reflectivity. Therefore, in this work, we studied the adsorption capacity of diaminomeleodinitrile on the surface of nickel from borate buffer solution in the cathodic and anodic regions. The values of its free adsorption energy were determined, which were at a potential of -0.65 V - 39.7 kJ / mol, and at 0.2 V - 66.2 kJ / mol. It was determined that diaminomeleodinitrile has adsorbed on the surface of nickel from borate buffer solution at pH = 7.4 mainly due to the forces of chemical interaction. It has been established that on the oxidized nickel surface, the adsorption of diaminomeleodinitrile begins in the region of lower concentrations compared to the “clean” surface. On average, a monolayer has formed within 60-75 min, while changes in the phase angle of the reflected light are small, due to the small size of the adsorbed molecule. It was determined that on the oxidized surface these changes are more than on the “clean” one. By method of reflective ellipsometry, which allows to measure and analyze the differences in the polarization parameters of a plane polarized light flux incident at an angle on two homogeneous media with different optical properties, the thickness of the resulting monolayer was determined. On an oxidized surface, it was ~ 0.5 nm, and on a “clean” surface, ~ 0.2 nm. When comparing these thicknesses with the size of the diaminomeleodinitrile molecule, it can be assumed that at a potential of 0.2 V, the diaminomeleodinitrile molecules are drawn out at an angle to the nickel surface, and at a potential of -0.65 V they are adsorbed flat on the nickel surface.

Nitro-substituted 2,3,7,7,8,12,18-hexamethyl-5-phenyl-13,17-diethylporphins with nitro groups in positions 10 and 20 of the porphyrin core and in the para-position of the benzene ring have been synthesized. The structure of the obtained compounds has been confirmed by H-1 NMR, UV, and IR spectroscopy as well as mass spectrometry. The kinetics of dissociation of zinc, copper, cobalt, and manganese complexes of the obtained porphyrins in proton-donor media has been studied. The stability of the porphyrin metal complexes has been related to the electronic effects of the substituents in the tetrapyrrole cycle and spatial distortion of the latter.

Immobilization of tetra-tert-butylphthalocyanine and its copper complex on a chemically activated surface of nonwoven polypropylene and Dacron materials was studied with the aim of creating new materials with antimicrobial properties. A method of the chemical activation of the surface of the studied materials by aminolysis was developed. It was shown that chemical activation leads to a change in the roughness of the polymer surface and formation of nitrogen-containing surface functional groups, which increases the sorption capacity of the studied materials. The modified non-woven materials exhibit a sustained antimicrobial activity.

The state of tetra(1,2,5-thiadiazolo)porphyrazine in a dimethyl sulfoxide medium is investigated. Relatively high stability is observed for the resulting proton-transfer complex, and a chemical structure is proposed for it. It is shown that the nature of the substituent in the porphyrazine macrocycle influences the kinetic parameters of the destruction of tetra(1,2,5-thiadiazolo)porphyrazine, tetra(5- tert -butylpyrazino) porphyrazine, octaethyltetrapyrazinoporphyrazine, and octaphenyltetrapyrazinoporphyrazine in a nitrogen-containing base–dimethylsulfoxide system. The effect the NH acidity of the porphyrazine macrocycle and the nature of the nitrogenous bases have on the reaction rate and activation parameters of the destruction of β,β-annelated porphyrazine proton-transfer complexes is established.

The methods of surface activation of nonwoven Dacron through aminolysis and the methods of immobilization of tetra-4-tert-butyl-, tetra-4-sulfo-, tetra-4-(carboxymethyl)phthalocyanines and their nickel, cobalt and copper complexes on activated materials are described. The state of the surface of the activated materials was studied by IR spectroscopy. Analysis of the electronic absorption spectra of the immobilized phthalocyanines revealed a monomolecular dispersion of tetra-4-tert-butyl-phthalocyanine and its complexes on the surface of nonwoven Dacron. By contrast, tetra-4-sulfo- and tetra-4-(carboxymethyl)phthalocyanines and their complexes are strongly associated. The catalytic activity of the obtained materials in the oxidation of sodium diethyldithiocarbamate with atmospheric oxygen was studied to find that the phthalocyanine ligands and their nickel and copper complexes are catalytically inactive. It was shown that the materials modified by the cobalt complexes accelerate the oxidation reaction 10–15 times.

5-[4'-(1,3-Benzothiazol-2-yl)phenyl]-2,3,7,8,12,18-hexamethyl-13,17-di-n-amyl-porphirin was synthesized and its coordination properties with the acetates of cobalt, copper and zinc in acetic acid and pyridine were investigated. On the base of data obtained the kinetic parameters of the complexation reaction were calculated. It was established that in acetic acid the increase in a rate of reaction of complexation is observed in the series: Co+2 < Zn+2 < Cu+2, while the activation energy decreases by a factor of 1.5-2 and the value of preexponential factor is significantly increased. The pyridine is an inverse relationship. Copper and cobalt complexes of porphyrin were used for surface modification of chemically activated polypropylene materials. Based on the electronic spectra, the effective surface concentration of immobilized porphyrin molecules was calculated. It was shown, that there is a direct dependence of the amount of grafted metal complexes on the surface structure of the polymer-carrier and conditions of immobilization of macromolecules. The obtained modified materials were tested for bioactivity with the use of an aqueous suspension of agar-agar infected on the following cultures: Staphylococcus aureus (gram-positive culture) and Escherichia coli (gram-negative culture) in the microbial load of 106 cells/ml. The results of the studies were showed that the obtained materials have bacteriostatic resistance to all types of used pathogens.Forcitation:GornukhinaO.V., VershininaI.A., KiselevA.N., KuvshinovaE.M., SyrbuS.A., GolubchikovO.A. 5-[4'-(1, 3-Benzothiazol-2-yl)phenyl]-2,3,7,8,12,18-hexamethyl-13,17-di-n-amylporphirin: synthesis, coordinationpropertiesandsorptiononpolypropylenematerials. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 1. P. 49-54

The paper presents the methods of synthesis of dimeric and trimeric compounds formed by donor–acceptor interactions of ZnII, MnIII, and SnIV porphyrin complexes. The structure of the porphyrin ensembles was determined by 1H NMR spectroscopy. The extra coordination properties of the synthesized dimeric and trimeric supramolecular systems in relation to nitrogen-containing compounds were studied and the stability constants of the resulting porphyrin extra complexes were determined.

A methodology of the synthesis of 4-(8-quinolylazo)resorcinol (QAR) and 1-(8-quinolylazo)-2-naphthol (QAN) was developed. The synthesized compounds were used to modify an oxidized charcoal sorbent. The sorbent efficiently adsorbs copper(II) and zinc(II) cations to form surface electroneutral chelate complexes. The conditions of sorption and desorption of zinc(II) and copper(II) were studied.

The immobilization of 5,10,15,20-tetrakis(4’-carboxy-phenyl)porphyrin on the surface modified polypropylene films was investigated. To activate the surface of the polypropylene the method of structural-chemical modification of the acrylamide and polyvinyl alcohol developed, which can increase the number immobilizing porphyrin 15–20 times. Modified materials possess of antimicrobial activity.

The experimental results showing a possibility of obtaining the combined materials on the basis of polymers with chemically activated surface and 3,7,13,17-tetramethyl-2,8,12,18tetraethyl-5,15-bis(4'-nitrophenyl) porphyrine and its copper complex are presented. The chemical activation of polymers was shown to result in a change in topography and chemical structure of a near-surface layer. By means of the new functional groups formed on a surface of polymeric matrixes the immobilization of 3,7,13,17-tetramethyl-2,8,12,18-tetraethyl-5,15-bis(4'-nitrophenyl)porphyrine and its copper complex was carried out, and the number of the immobilized compounds was determined. It is shown that conditions of preliminary activation of polymeric matrixes, and conditions of immobilized porphyrine and its copper complex strongly affect efficiency of their binding with a polymeric surface. Research of anti-microbe activity of the modified materials in relation to gram-negative and gram-positive microorganisms was conducted. As the results of the conducted microbiological research it was established that the received materials possess the expressed anti-microbe activity. And, the samples modified by a copper complex show twice greater bactericidal activity than modified by ligands.

The experimental results of surface modification of cellulose materials with medicinal preparations of cefazolin and dioxydinum are presented. Modified materials were shown to have clearly defined antimicrobial and anti-inflammatory activity. They can be recommended for the creation of new suture material for veterinary science.

The experimental results, which show the possibility of immobilization of tetra(4-tert-butyl)phthalocyanine complex and its zinc complex on the surface of nonwoven polypropylene and lavsan materials. The alkali etching method was used for activation of the polypropylene surface. It was shown that the modified polymeric materials possess sorption activity relative to creatinine.

The features of the acid-base interaction of tetra-(4-tert-butyl)-tetrabenzoporfirazin with nitrogen-containing bases in dimethylsulfoxide were investigated. Complex materials such as polymer type tetra-(4-tert-butyl)tetrabenzoporphyrazin were obtained. The modified polymeric materials were shown to have the sorption activity in relation to the nitrogenous bases.

The process of immobilization of cobalt(II) 5,10,15,20-tetrakis(4-methylpyridyl)porphyrin tetratosylate on chemically activated surface of polypropylene materials was studied using infrared spectroscopy of multiple frustrated total internal reflection, electron spectroscopy, and atomic force microscopy. The modified materials were shown to have a sorption activity with respect to nitrogen bases, the structural analogs of blood toxines.