THEORETICAL BASIS OF CHEMICAL TECHNOLOGY
- Silicone aluminum phosphate molecular sieves SAPO-11 containing 0.5 wt % Pt on the surface were obtained from gels.
- As the SiO2/Al2O3 ratio increases, the number of acid centers increases. This then leads to an increase in the conversion of n-hexadecane.
- The selectivity of the formation of hydrocarbons of the structure decreases at the same time.
Objectives. To obtain silicone aluminum phosphate molecular sieves SAPO-11 with different silicon content, to determine their pore space and acidic properties, to apply 0.5 wt % to their surface Pt, and to evaluate the effectiveness of the use of n-hexadecane in the hydroisomerization reaction.
Methods. The chemical composition of the SAPO-11 molecular sieves obtained was determined by means of X-ray fluorescence spectroscopy using a Shimadzu EDX-7000P device. The radiographs of non-calcined SAPO-11 were recorded on a Shimadzu XRD-7000 diffractometer in CuKα radiation.
Results. Silicone aluminum phosphate molecular sieves SAPO-11 containing 0.5 wt % Pt on the surface were obtained from gels. As the SiO2/Al2O3 ratio increases, the number of acid centers increases. This then leads to an increase in the conversion of n-hexadecane. The selectivity of the formation of hydrocarbons of the structure decreases at the same time.
Conclusions. Silicone aluminum phosphate molecular sieves Pt-SAPO-11 were obtained. It was also found that the samples undergo n-hexadecane conversion.
- Arrays of calculated data were obtained with regard to molar enthalpies of vaporization for 25 compositions of binary azeotropes (isothermal, isobaric conditions of phase equilibrium), and the full range of compositions of the benzene–ethanol system at atmospheric pressure.
- The accuracy of thermodynamic methods for calculating the vaporization enthalpy of binary azeotropic mixtures according to vapor–liquid equilibrium data is higher in 85% of cases for isothermal, and in 75% of cases for isobaric conditions.
- By taking into account the influence of temperature on the activity coefficients of components in the liquid phase, the values of excess molar enthalpy both for azeotrope compositions and for the full concentration range of the benzene–ethanol system under isobaric conditions of liquid–vapor phase equilibrium can be accurately reproduced.
Objectives. To calculate the molar enthalpy of vaporization of binary homogeneous mixtures based on isothermal and isobaric vapor–liquid equilibrium data, and to compare the results of calculation of molar enthalpy of vaporization by different methods with experimental data.
Methods. Simulation of the vapor–liquid equilibrium of binary systems according to the Non-Random Two Liquid “local compositions” equation and thermodynamic calculations of molar vaporization enthalpies of binary mixtures at different conditions of vapor–liquid equilibrium were used.
Results. Arrays of calculated data were obtained with regard to molar enthalpies of vaporization for 25 compositions of binary azeotropes (isothermal, isobaric conditions of phase equilibrium), and the full range of compositions of the benzene–ethanol system at atmospheric pressure.
Conclusions. The accuracy of thermodynamic methods for calculating the vaporization enthalpy of binary azeotropic mixtures according to vapor–liquid equilibrium data is higher in 85% of cases for isothermal, and in 75% of cases for isobaric conditions. By taking into account the influence of temperature on the activity coefficients of components in the liquid phase, the values of excess molar enthalpy both for azeotrope compositions and for the full concentration range of the benzene–ethanol system under isobaric conditions of liquid–vapor phase equilibrium can be accurately reproduced.
CHEMISTRY AND TECHNOLOGY OF ORGANIC SUBSTANCES
- Previously unknown substances and compounds containing nitrogen-containing organosilicon products as components of the curing composition were obtained. Their physicomechanical and operational properties were examined, including the possibility of using them as filling heat-resistant and fire-resistant compositions for sealing high-voltage and high-frequency equipment.
- It was shown that nitrogen-containing organosilicon compounds—3-(diethylamino)-2-[(triethoxysilyl)oxy]propyl-2-methacrylate and triethoxysilyl ester of γ-triethoxysilylpropyl-carbamic acid—can be used as part of a curing system together with bromine-containing fillers, in order to obtain compounds used for filling high-voltage high-frequency transformers, throttle valves, and other electronic equipment elements with non-combustible properties and increased heat resistance.
Objectives. To study the possibility of using nitrogen-containing organosilicon compounds in the creation of heat-resistant and fireresistant casting compositions to seal high-voltage high-frequency equipment.
Methods. Nitrogen-containing organosilicon compounds were obtained using the N-siloxycarbonylation, formylation, and silylation methods. The methods used in the work were infrared spectroscopy, elemental analysis, viscometry, and differential scanning calorimetry. The mechanical and dielectric properties of the samples were determined.
Results. Previously unknown substances and compounds containing nitrogen-containing organosilicon products as components of the curing composition were obtained. Their physicomechanical and operational properties were examined, including the possibility of using them as filling heat-resistant and fire-resistant compositions for sealing high-voltage and high-frequency equipment.
Conclusions. It was shown that nitrogen-containing organosilicon compounds — 3-(diethylamino)-2-[(triethoxysilyl)oxy]propyl-2-methacrylate and triethoxysilyl ester of γ-triethoxysilylpropyl-carbamic acid — can be used as part of a curing system together with bromine-containing fillers, in order to obtain compounds used for filling high-voltage high-frequency transformers, throttle valves, and other electronic equipment elements with non-combustible properties and increased heat resistance.
CHEMISTRY AND TECHNOLOGY OF MEDICINAL COMPOUNDS AND BIOLOGICALLY ACTIVE SUBSTANCES
- Platinum(II) complexes of pyridine-containing derivatives of natural chlorins were obtained for application in combination therapy in oncology. The schemes for synthesizing the target photosensitizers were optimized, in order to increase the yields and for subsequent transfer to industrial sites.
- It was found that pyridine-containing derivatives of natural chlorins could be obtained in high yields, that they possess chelating properties for platinum, and can be considered as binary agents in cancer therapy after successful preclinical trials.
Objectives. To synthesize Pt-containing derivatives of natural chlorins as potential agents for the combination therapy in oncology. Platinum compounds are known to occupy an important place as chemotherapeutic agents in the treatment of oncological diseases. However, Pt(II) complexes are highly toxic to the body and are not selectively accumulated in tumor cells. If photodynamic and chemotherapy methods are combined in a single drug, the pigments are responsible for the selectivity of conjugate accumulation in the tumor, while a chemotherapeutic agent based on Pt(II) complexes is responsible for the cytotoxic effect on tumor cells. This will not affect healthy cells and thereby minimize the systemic toxicity of the drug to the body.
Methods. Methods for the synthesis of pyridine-containing derivatives of natural chlorins and their metal complexes for use as potential binary agents in oncology were applied. As part of the study, the structures of the compounds obtained were confirmed by mass spectrometry, nuclear magnetic resonance spectroscopy, ultraviolet spectroscopy, and high-resolution chromatography-mass spectrometry. Preparative methods, including thin-layer and column chromatography, centrifugation and recrystallization, were used to isolate and purify the compounds obtained.
Results. Platinum(II) complexes of pyridine-containing derivatives of natural chlorins were obtained for application in combination therapy in oncology. The schemes for synthesizing the target photosensitizers were optimized, in order to increase the yields and for subsequent transfer to industrial sites.
Conclusions. It was found that pyridine-containing derivatives of natural chlorins could be obtained in high yields, that they possess chelating properties for platinum, and can be considered as binary agents in cancer therapy after successful preclinical trials.
- The optimal parameters for obtaining powders for inhalation were found by means of mathematical statistics: air flow rate was 37 m3/h; compressed air flow rate — 601 L/h; inlet air temperature — 150°C; solution flow rate — 45% of the power of the peristaltic pump (16.3 g/min for this composition); L-leucine concentration — 10 wt %; ratio of components of the matrix polyvinylpyrrolidone K-30/D-mannitol = 1 : 3.
- Under these conditions, as well as by means of 2 experiments additionally selected from the research design, a composition with the active substance isoniazid was spray dried. The resulting powders were analyzed, in order to confirm the correctness of the recommended parameters.
Objectives. To study the influence of the type of matrix-forming material and excipients concentration, spray drying parameters on the characteristics of the powder for inhalation, as well as to investigate the inhalation compositions for stability under stressful conditions.
Methods. Spray drying was used to obtain powder compositions with the required characteristics for inhalation therapy. Microscopic and analytical studies of powders were carried out. Statistical analysis made it possible to estimate the influence of factors on the powder characteristics and rank them by importance. The stability of spray dried powders was studied.
Results. The optimal parameters for obtaining powders for inhalation were found by means of mathematical statistics: air flow rate was 37 m3/h; compressed air flow rate — 601 L/h; inlet air temperature — 150°C; solution flow rate — 45% of the power of the peristaltic pump (16.3 g/min for this composition); L-leucine concentration — 10 wt %; ratio of components of the matrix polyvinylpyrrolidone K-30/D-mannitol = 1 : 3. Under these conditions, as well as by means of 2 experiments additionally selected from the research design, a composition with isoniazid as an active substance was spray dried. The resulting powders were analyzed, in order to confirm the correctness of the recommended parameters.
Conclusions. The selection of compositions and spray drying conditions involves multiple criteria. The characteristics of the powder for inhalation may deteriorate significantly during long-term storage. The optimal parameters were determined using statistical analysis and confirmed by experimental data.
CHEMISTRY AND TECHNOLOGY OF INORGANIC MATERIALS
- Cold sintering enables the formation of single-phase corundum ceramics with an open porosity of 47.9% directly from the initial boehmite powder with the addition of 5 wt % corundum in the presence of 20 wt % water at a temperature of 450°C, mechanical pressure of 220 MPa, and isothermal exposure for 30 min.
- Under the same conditions of cold sintering, a mixture of diaspore and boehmite was transformed into α-AlOOH ceramics. This then turned into corundum with an open porosity of 39% when calcined in air at 600°C for 1 h.
- The resulting materials had permeability for pure water above 5000 L/(m2∙h∙bar).
Objectives. To obtain porous corundum ceramics using an innovative cold sintering process starting from different phase modifications of aluminum oxohydroxide — boehmite γ-AlOOH and diaspore α-AlOOH; to study the phase and structural properties of the resulting materials; and to assess their permeability to water.
Results. Cold sintering enables the formation of single-phase corundum ceramics with an open porosity of 47.9% directly from the initial boehmite powder with the addition of 5 wt % corundum in the presence of 20 wt % water at a temperature of 450°C, mechanical pressure of 220 MPa, and isothermal exposure for 30 min. Under the same conditions of cold sintering, a mixture of diaspore and boehmite was transformed into α-AlOOH ceramics. This then turned into corundum with an open porosity of 39% when calcined in air at 600°C for 1 h. The resulting materials had permeability for pure water above 5000 L/(m2∙h∙bar).
Conclusions. Cold sintering is a promising approach to producing porous corundum ceramics which can be used in filtration systems. Compared to traditional ceramic technology, the new approach reduces energy, time, and labor costs in the material manufacturing. It also eliminates the need to use auxiliary substances (binders, pore-forming agents, etc.).
SYNTHESIS AND PROCESSING OF POLYMERS AND POLYMERIC COMPOSITES
- Based on the example of large-scale production thermoplastics, it was shown that a combination of technological methods of stacking, perforation, and local plasticization of films of transparent thermoplastic polymers can produce pleochroic multicolor materials for a range of human activities.
- The possibility of hidden coding of information on multilayer packaging materials, and its visualization and instrumental reading in polarized light was confirmed by color differential and contrast of 150 and 60 units, respectively.
- It was also shown that several monochrome tones of different lightness and brightness can be obtained by varying the number of layers or perforating the films in multilayer materials.
Objectives. To develop technologies for producing multilayer films of transparent thermoplastic polymers; to study methods of modifying their supramolecular structure; and to determine their optical properties by means of optical-polarization methods for the use of modified films as decorative and design materials in modern architecture.
Methods. Industrial samples of polystyrene, low-density polyethylene, polypropylene, and polyvinyl chloride films from various manufacturers (Don Polimer, Vektor, and Sibur) were the objects of the study. The optical properties of the films were studied by means polarized-light spectrophotometry. In order to modify the supramolecular structure of the polymers, the surfaces of the films were treated under isometric conditions with volatile solvents or their aqueous solutions. Parts of the layers of multilayer films were removed by cutting with a punching knife using a press or with a manual device for perforating printing materials.
Results. The spectral characteristics of multilayer films of several transparent thermoplastic polymers in polarized light were determined. The study showed that a wide palette of colors and contrasting images can be obtained by mechanically removing part of the layers of multilayer films. The phenomenon of pseudo-disappearance of the outermost layer was discovered after treatment of a stack of films under isometric conditions with volatile solvents or their aqueous solutions.
Conclusions. Based on the example of large-scale production thermoplastics, it was shown that a combination of technological methods of stacking, perforation, and local plasticization of films of transparent thermoplastic polymers can produce pleochroic multicolor materials for a range of human activities. The possibility of hidden coding of information on multilayer packaging materials, and its visualization and instrumental reading in polarized light was confirmed by color differential and contrast of 150 and 60 units, respectively. It was also shown that several monochrome tones of different lightness and brightness can be obtained by varying the number of layers or perforating the films in multilayer materials.
- It was found for the first time that condensation products of D,L-camphor and p-ethoxyaniline exhibit a stabilizing effect in formulations of rubbers based on polar nitrile butadiene rubber.
- Conclusions. According to the results of laboratory and in situ tests, the study established that the use of N-[(1RS,2RS)-camphan-2-yl]-4-ethoxyaniline (reduced form) as an antifatigue agent is preferable. This is due to the presence of a mobile hydrogen atom at the nitrogen atom. The protective effect is manifested in terms of the better preservation of elastic-strength properties of rubbers with less change in hardness.
Objectives. To investigate the protective efficacy of unreduced and reduced forms of the condensation product of D,L-camphor and p-ethoxyaniline in nitrile butadiene rubber formulations when compared with the conventional stabilizer N-isopropyl-N′-phenyl- p-phenylenediamine aged under laboratory and in situ climatic conditions in the tropics.
Methods. The thermostabilizing effect of the condensation product of D,L-camphor and p-ethoxyaniline was evaluated by means of infrared spectroscopy using the dynamics of changes in the absorption bands of carbonyl and hydroxyl groups. The features of rubber vulcanization were studied by means of rotorless rheometry. Changes in the physical and mechanical properties of rubbers and degree of cross-linking were evaluated after thermo-oxidative aging in laboratory conditions. They also took into account the results of longterm exposure of samples in undeformed and deformed state in a tropical climate, taking into account meteorological data of the Can Gio climatic testing station.
Results. It was found for the first time that condensation products of D,L-camphor and p-ethoxyaniline exhibit a stabilizing effect in formulations of rubbers based on polar nitrile butadiene rubber.
Conclusions. According to the results of laboratory and in situ tests, the study established that the use of N-[(1RS,2RS)-camphan-2-yl]- 4-ethoxyaniline (reduced form) as an antifatigue agent is preferable. This is due to the presence of a mobile hydrogen atom at the nitrogen atom. The protective effect is manifested in terms of the better preservation of elastic-strength properties of rubbers with less change in hardness.
ANALYTICAL METHODS IN CHEMISTRY AND CHEMICAL TECHNOLOGY
- The paper presents a new method for determining the gross content of inorganic iodine in Laminariae thalli L.
- This technique can be used not only in scientific research, but also in the routine quality control of medicinal plant raw materials in control and analytical laboratories engaged in pharmaceutical quality control.
Objectives. To develop and validate a methodology for determining inorganic iodine in Laminariae thalli L., corresponding to the norms of the State Pharmacopoeia of the Russian Federation, 15th edition (SPh 15). The methodology needs to be valid and suitable for the quality control of pharmaceutical raw materials in factory laboratories.
Methods. Cathode inversion voltammetry was used as an instrumental method for determining inorganic iodine using a graphite electrode capable of sorbing electroactive ion associates of surfactant–iodine.
Results. When compared with the titrimetric technique recommended by SPh 15, the proposed technique is more selective, sensitive and less time-consuming. The efficiency and metrological characteristics of the technique were confirmed by validation in accordance with the requirements of SPh 15.
Conclusion. The paper presents a new method for determining the gross content of inorganic iodine in Laminariae thalli L. This technique can be used not only in scientific research, but also in the routine quality control of medicinal plant raw materials in control and analytical laboratories engaged in pharmaceutical quality control.
ERRATUM
ISSN 2686-7575 (Online)