Vol 13, No 3 (2023)
Chemical Sciences
Synthesis of the Ultem series polyetherimides
Abstract
Polyetherimides (PEIs) are a class of structural polymers with the most successful combination of such essential properties for practical applications as high heat resistance, thermal stability, ultimate tensile strength, elastic modulus, good dielectric properties, and high chemical and radiation resistance. However, along with these advantages, PEIs are compounds with high softening and melting points, which complicates their processing into products. In recent decades, specialists have found numerous ways to decrease the glass transition temperature by increasing the flexibility of the main polymer chain. To this end, functional groups with a higher degree of rotation, such as isopropylidene, hexafluoroisopropylidene, 1,2-dichloroethylene, and other substituents, are introduced into the main polymer chain. Polyetherimide, whose precursors are 3(4)-nitrophthalic anhydride, m-phenylenediamine, and bisphenol A, was first produced by General Electric under the Ultem brand name and is currently believed to be one of the best-known engineering thermoplastics. In particular, two synthetic methods can be used to obtain such polyetherimides. The first technique uses a cyclization of poly(amidocarboxylic acid), which is obtained by the polycondensation of dianhydride of 2,2-bis-[4-(3,4-dicarboxyphenoxy)phenyl]propane and m-phenylenediamine. The second technique uses the polynitro substitution of 1,3-bis[N-(3-nitrophthalimido)]benzene and the dynatrium salt of bisphenol A. To date, the Russian scientific literature lacks reviews with detailed descriptions of known methods for the preparation of Ultem series polyetherimides. The present review generalizes and systematizes the available literature data regarding the synthesis of the Ultem series PEIs. In addition, this study describes preparation methods of soluble thermoplastic polyetherimides of this series, available synthesis methods of initial monomers with reaction yields, and physical characteristics of such polymers.
Izvestiya Vuzov. Prikladnaya Khimiya i Biotekhnologiya. 2023;13(3):325-332
325-332
Synthesis, homopolymerization and properties of p-aminopyridine methacrylate
Abstract
For the first time, p-aminopyridine methacrylate was synthesized by a reaction between p-aminopyridine and methacryloyl chloride. IR and NMR spectroscopy сonfirmed the obtained compound structure. Radical homopolymerization of synthesized p-aminopyridine methacrylate was carried out either in bulk or in benzene solution (initiator – AIBN). The study of radical polymerization regularities of p-aminopyridine methacrylate discovered no side reactions and induction period of the reported process under the created conditions with a maximum yield of 92%. It was found that p-aminopyridine methacrylate is a more reactive monomer in radical polymerization as compared to methyl methacrylate. The structure of the obtained monomer and polymer was investigated by IR and NMR spectroscopy. Based on these data, the polymerization proceeds by a double bond, with substituents in the side macro chain remaining unreacted. The study of the synthesized monomer polymerization in the bulk indicated the presence of the gel effect. The autoacceleration begins at ~25% monomer conversion during the polymerization process, which agrees with the literature data. It was discovered that the polymerization of p-aminopyridine methacrylate proceeds at a rate higher than that of methyl methacrylate. This observation is likely to be connected with the substituent contribution to the electronic state of the entire monomer molecule. Hence, the electron density of the vinyl group changes and the growing radical becomes stabilized with the substituent –M-effect. The polymer synthesized possesses high antimicrobial properties.
Izvestiya Vuzov. Prikladnaya Khimiya i Biotekhnologiya. 2023;13(3):333-339
333-339
Physico-chemical biology
Enzymatic activity of extracts from higher fungi for manufacturing fermented dairy products
Abstract
The present study investigates the enzymatic activity and chemical composition of extracts obtained from the substrate mycelium of higher fungi. The investigated object is the biomass of fungi Piptoporus betulinus (substrate mycelium) gathered after solid-phase cultivation on natural substrate. The extracts were obtained using distilled water (pH=7.0), acetate (pH=4.7) and phosphate (pH=7.4) buffers, and Mcllvaine buffer (pH=4.0). Milk-clotting, proteolytic, cellulosolytic and lipolytic activity, as well as protein content, were determined in both aqueous or buffer extracts. As a result, the values of cellulosolytic (3.75–3.90 units/g), lipolytic (40.00–44.24 units/g) and milk-clotting (65.80–66.60 units/mL) activity of the substrate mycelium was determined. These values differ slightly in the extracts prepared on distilled water and buffers. Moreover, the concentration of protein substances in the native aqueous extract from the substrate mycelium of P. betulinus was 14.50 mg/mL. The values of proteolytic activity varied from 0.22 to 0.78 units/mL. Distilled water was found to be the most effective solvent for achieving high values of milk-clotting activity. Extract purification by microfiltration or with bentonite leads to a significant decrease in protein concentration (up to 5.90 mg/mL), cellulose(up to 1.40 units/g), lipo(up to 5.30 units/g), and proteolytic (up to 0.11 units/mL) activity, and an increase in milk-clotting activity values (up to 285.80 units/mL). The bentonite sorbs cellulosolytic, lipolytic, and non-specific proteolytic enzymes, resulting in a noticeable increase in the value of milk-clotting activity. In the aqueous extract of P. betulinus fungi, a high ratio of milk-clotting to proteolytic activity was found with a value of 2598.20. This may lead to an increased yield and improvement of the organoleptic properties of cheese and its storage period.
Izvestiya Vuzov. Prikladnaya Khimiya i Biotekhnologiya. 2023;13(3):340-349
340-349
Variety-strain interaction specificity of Bacillus subtilis with salt-stressed Phaseolus vulgaris L. plants
Abstract
The effectiveness of crop inoculation using growth-stimulating bacteria can depend on the plant variety and environmental conditions. The reactions of three-week-old plants of the Ufimskaya and Zolotistaya green bean varieties to inoculation with strains 26D and 10-4 in normal conditions and under stress (1% NaCl 48 h) were analysed. Although the Zolotistaya variety formed less biomass and leaf area, it surpassed the Ufimskaya variety in terms of chlorophyll and root water content, as well as reacting to stress by reducing the content of photosynthetic pigments and root water content. Inoculation contributed to the preservation of these indicators at the level of non–stressed plants: the positive effect of strain 26D was expressed in the effect on the composition of pigments, while that of strain 10-4 was expressed in the hydration of roots. Under stress, the Ufinskaya variety improved the water status of the roots, on which inoculation had a weak or negative effect; however, the decrease in the level of synthetic pigments under stress was compensated by inoculation with both strains. According to the biomass of three-week-old plants, the Zolotistaya variety was shown to respond positively to inoculation with both strains both normally and under stress, while the Ufimskaya variety tended to react negatively to inoculation with strain 26D; under stress, the effect of inoculation with both strains was positive. Compared with the stress-induced control, the malondialdehyde content in the roots of inoculated plants of both varieties decreased in comparison with that of the uninoculated control both in normal conditions and under stress. The revealed differences in plant reactions to inoculation serve as a basis for further analysis of the effectiveness of variety-strain combinations of symbiotic partners.
Izvestiya Vuzov. Prikladnaya Khimiya i Biotekhnologiya. 2023;13(3):350-358
350-358
Catalytic properties and immobilization of enzyme preparations containing lipase of the haloalkalotolerant bacteria Pseudomonas peli and Bacillus aequororis
Abstract
In this work, we investigate the catalytic properties and immobilization of enzyme preparations containing lipase of haloalkalotolerant bacteria Pseudomonas peli and Bacillus aequororis. Lipase was isolated from the P. peli 3-T and B. aequororis 5-DB followed by its immobilization on either carboxymethylcellulose, activated chitosan or fodder yeast. The pH-dependence of native enzyme activity and thermostability, as well as the residual activity upon immobilization and drying of immobilized product, were determined. The lipase activity from both sources enhances with increasing alkalinity of the reaction medium. Specifically, P. peli 3-T lipase exhibited no activity in an acidic medium, and B. aequororis 5-DB lipase exhibited around 20% of maximum activity at a pH value of 6–7. The isolated lipase has a rather high thermostability; thus, P. peli 3-T lipase fully retains its initial activity upon heating to 60°C and 70°C for 1 h. Moreover, 15 min exposure to temperatures of 80°C and 90°C leads to an activity decrease of 73% and 83%, respectively. Activated chitosan and fodder yeast are the most promising of the studied excipients for enzyme immobilization. Drying of the immobilized lipase product on the activated chitosan showed retention of 3% and 46% of the native enzyme activity derived from P. peli 3-T and B. aequororis 5-DB, respectively. In the case of fodder yeast, these values were 2% and 64%, respectively.
Izvestiya Vuzov. Prikladnaya Khimiya i Biotekhnologiya. 2023;13(3):359-369
359-369
Effects of the anionactive surfactant sodium dodecyl sulfate on the adhesion of cells of the strain Micrococcus luteus 1-i to the surface of carbon materials
Abstract
The adhesion of microorganisms on various surfaces plays a crucial role in many biotechnological processes. A widespread component of wastewater is the anion-active surfactant sodium dodecyl sulfate (SDS). Surfactants have a significant influence on all interfacial reactions, including those occurring in microbial fuel-cell technology. The work set out to study the effect of sodium dodecyl sulfate on the sorption of cells of the Micrococcus luteus 1 strain (which has electrogenic activity in microbial fuel cells) on the surface of various carbon-containing electrode materials used in biological fuel cell technology: 1) carbon tissue; 2) carbon felt; 3) crushed graphite contact trolleybus inserts (summer); 4) birch activated carbon. Using spectrophotometry and microscopy methods, the presence of sodium dodecyl sulfate in the concentration range of 10–200 mg/l was shown to increase the sorption of Micrococcus luteus 1-i cells on the surfaces of the tested carbon materials under experimental conditions. The maximum increase in sorption during 2 hours of exposure was detected when 100 mg/l of this surfactant was applied: for birch activated carbon – 21%; for carbon fabric – 26%; for carbon felt relative to the control (without surfactant) – 24%. The results demonstrate a sufficiently effective adhesion of Micrococcus luteus 1-i cells to various carbon materials, including in the presence of fairly high concentrations of sodium dodecyl sulfate, confirming the prospects of this strain for use in various types of microbial fuel cells.
Izvestiya Vuzov. Prikladnaya Khimiya i Biotekhnologiya. 2023;13(3):370-381
370-381
Determining the fatty acids, polar and non-polar volatile organic compounds of the veterinary preparation “Trametin Plus”
Abstract
For the prevention and treatment of associated gastrointestinal and respiratory diseases of growing stock, a new veterinary preparation “Trametin Plus” is proposed. This drug is obtained from fungi-xylotrophs using biotechnology methods. The properties of such preparations depend on bioactive substances included in their composition.Available publications present miscellaneous information on the lipogenesis features and fatty acids composition synthesized by wood-destroying fungi. In this work, we study the qualitative and quantitative composition of fatty acids and analyze volatile polar and non-polar organic compounds of “Trametin Plus”. The total concentration of fatty acids was found to be 70 µg/g, with 50.0% being free acids and 50.0% being their esters. Squalene was established to be the most dominant non-polar volatile component. Concerning the minor non-polar volatile components of “Trametin Plus”, these are amino acids with a low molecular weight, such as glycine, arginine and β-alanine. The analysis confirms the multicomponent composition of the preparation, which accounts for its diverse biological properties, namely antibacterial, antiviral, antioxidant and immune-boosting activity. These properties determine the high health-promoting efficacy of the studied veterinary preparation.
Izvestiya Vuzov. Prikladnaya Khimiya i Biotekhnologiya. 2023;13(3):382-391
382-391
Synthesis of cellulose nitrates from Miscanthus × giganteus var. KAMIS cellulose obtained under pilot production conditions
Abstract
The work is devoted to the study of a novel national raw material resource Miscanthus × Giganteus var. KAMIS, which is positioned as one of the most promising natural sources for obtaining high-quality cellulose for the purpose of its further chemical functionalisation. A batch of technical cellulose isolated from raw materials under pilot production conditions using the nitric acid method having a cellulose content of 50.2% was characterized by high α-cellulose mass fraction (92.8%) and degree of polymerisation (1200) values. On the basis of the pilot batch of technical cellulose, a sample of cellulose nitrates offering basic functional properties was obtained: mass fraction of nitrogen – 11.18%; viscosity – 48 MPa·s; solubility – 94%. The synthesised sample is characterized by extremely high solubility in acetone, confirming the production of cellulose nitric acid esters, and a high yield of 150%. IR-Fourier spectroscopy was used to identify the main functional groups in the experimental batch of technical cellulose (3384, 2902, 1639, 1428, 1370, 1319, 1161, 700–500 cm-1) and in a sample of cellulose nitrates (1659, 1278, 834, 746, 683 cm-1). Acorresponding affiliation to cellulose and cellulose nitric acid esters was established. The structural and morphological features of the fibres of the experimental batch of technical cellulose and a sample of cellulose nitrates were characterised using scanning electron microscopy. Combined methods of thermogravimetric and differential thermal analyses were used to establish high initial temperature (197 °C) and specific heat of decomposition (6.92 kJ/g) values at the beginning of intensive decomposition. The obtained results substantiate the possibility to chemically functionalise cellulose isolated from a new alternative source into cellulose nitric acid esters with satisfactory functional properties.
Izvestiya Vuzov. Prikladnaya Khimiya i Biotekhnologiya. 2023;13(3):392-401
392-401
Carotenoid content in Prunus armeniaca L. apricot fruits depending on the extraction method
Abstract
In the middle of the 20th century, specialists of the Tsitsin Main Moscow Botanical Garden of the Russian Academy of Sciences collected a valuable apricot gene pool characterized by high diversity and winter hardiness. From this gene pool, L.A. Kramarenko carried out selection work to develop winter-hardy apricot varieties, such as Aisberg, Vodoley, Guiani, Lel’, Tsarsky and others, which were included in the State Register of Breeding Achievements of the Russian Federation. The use of these varieties in further selective breeding requires information on their carotenoid content. In this work, we determine carotenoids in apricot (Prunus armeniaca L., Rosaceae) fruits of Moscow breeding varieties Aisberg, Vodoley, Guiani, Lel’, Tsarsky and Zachat’ievsky. We employed different extraction methods of plant raw materials, contributing to the optimal extraction of carotenoids from apricot fruits. Extraction was performed with hexane, 96% ethanol at room temperature, and EtOH heated to 60°C (water bath) for 40 min. The highest carotenoid content was observed in Lel’ (31.73 mg%) and Vodoley (31.77 mg%) varieties, while the lowest content was observed in the Zachat’ievsky sample (11.93 mg%). The application of multiple solvents increases the reliability of determining carotenoids in plants for computational and experimental studies. The discovered range of their content can be used for description of promising forms during breeding works. In this way, new and beneficial for health varieties may emerge.
Izvestiya Vuzov. Prikladnaya Khimiya i Biotekhnologiya. 2023;13(3):402-408
402-408
Cell culture of Scorzonera hispanica L., strain SFR-SH1. Major secondary metabolites
Abstract
Plant cell cultures are widely used in the world pharmaceutical industry as a raw material for the production of biologically active compounds. Their certain advantages, such as independence from seasonal conditions, diseases and their transmitter, contribute to the development of this area of biotechnology. In addition, it is possible to obtain the required quantity of the desired product with standard quality characteristics. Since the biosynthesis of new compounds does not occur in the intact plant, another advantage of this method arises. It consists in obtaining new substances due to the peculiarities of cell culture biology. The conducted review represents secondary metabolites isolated from the cell culture of Scorzonera hispanica L., strain SFR-SH1, possessing biological activity. In addition, the history of developing the selected strain and schemes for isolation and purification of secondary metabolites are demonstrated. For a clearer discussion, the main secondary metabolites found in cells are broadly divided into three groups. The first group includes compounds typical of most plants: β-sitosterol and its glucoside, caffeic acid methyl ester and oleanic acid. The second group contains syringaresinol monoglucoside, which is relatively rare in plant objects. The third group includes two compounds isolated from natural objects for the first time: sesquiterpene glucoside, scorzoside and neolignan scorzonoside. The results obtained were compared with the available literature data on the chemical composition of native plants of S. hispanica and other Scorzonera genera species. Due to its high biological activity, Syringaresinol monoglycoside attracts more attention than other compounds detected in cultured cells. Long-term cultivation of Monoglycoside leads to an alteration in the physicochemical characteristics of this compound for an unknown reason.
Izvestiya Vuzov. Prikladnaya Khimiya i Biotekhnologiya. 2023;13(3):409-415
409-415
Supercritical extract from the Japanese sea brown algae Undaria pinnatifida as a source of bioactive compounds
Abstract
Bioactive compounds contained in algae have practical applications in the pharmaceutical industry, production of human food and animal feed, and other fields. Since brown algae contain a wide range of bioactive substances, producing high-quality and chemically safe extracts on their basis is an urgent task. This study was aimed at characterization of supercritical extract from the corresponding algae, as well as the identification and evaluation of the content of bioactive compounds. The content of carotenoids, phenolic compounds and mannitol was determined by UV-Vis spectroscopy; a fatty acid analysis was carried out by GLPC; the qualitative composition of carotenoids and phenolic compounds was analyzed by HPLC. Supercritical CO2 extraction of the brown alga U. rinnatifida with EtOH as a polar modifier is characterized by high ejection efficiency of fatty acids, phenolic compounds and carotenoids. The latter profile of the collected supercritical extract consists of 14 representatives. In particular, fucoxanthin (58.1% of the sum), zeaxanthin (12.6% of the sum), and fucoxanthinol (14.5% of the sum) are the most abundant compounds. Palmitic acid, oleic acid, arachidonic acid, and eicosapentaenoic acids are the main of the 20 fatty acids found in the corresponding extract. However, the class of polyunsaturated fatty acids is predominant, which content of the ώ-6 and ώ-3 groups does not differ significantly. The total content of phenolic compounds is 13.45+0.43 mg/g of gallic acid equivalent. For instance, the most represented phenolic substances are epicatechin, epigallocatechin gallate, syringic acid, coumaric acid, ferulic acid and salicylic acid.
Izvestiya Vuzov. Prikladnaya Khimiya i Biotekhnologiya. 2023;13(3):416-424
416-424
To the question of microsatellite associations of cultivated soybean of the Amur Oblast with agricultural traits
Abstract
This prospecting study evaluated the correlation strength between the length of microsatellite loci and valuable agricultural traits. For labeling the genetic systems of soybean varieties, DNA was isolated using a ready-made kit followed by subjecting the manufactured reaction mixture to standard PCR. In total, 15 primer pairs were used to analyze 18 varieties of the All-Russian Soybean Research Institute selection. Eight samples (Satt1, Satt2, Satt5, Satt9, Soyhsp176, Satt681, Satt141 and Satt181) were the most specific and fully suitable for the identification and certification of available soybean genotypes; however, sample Sat_263 was only partially applicable. The possible influence of loci on agricultural traits was determined by searching for associations of simple sequence repeats (SSRs) with quantitative trait loci (QTLs) in the NCBI and soybase databases. To identify the statistical relationship between different attributes and loci lengths, a correlation analysis was performed by calculating Pearson’s coefficient. This analysis revealed a direct relationship between the length of Satt5, Sat_263 and Satt181 loci and plant height, with an inverse relationship being observed in the case of Satt2. The mean value of the correlation coefficient (r) comprised 0.485, 0.55, 0.435 and -0.422, respectively. Samples Satt1(r = 0.561) and Satt2 (r = 0.562) indicate a direct correlation between their length and plant seed weight, while an inverse correlation was established in the case of Satt9 (r= -0.453) and Satt681 (r= -0.527). A weak inverse correlation was found with the trait of potential yield with Satt2 (r = -0.321). This indicates the ability of microsatellites to act as a marker of a particular trait.
Izvestiya Vuzov. Prikladnaya Khimiya i Biotekhnologiya. 2023;13(3):425-433
425-433
Increased Arabidopsis thaliana cell culture resistance to sodium fluoride by constitutive expression of HSP101
Abstract
Fluorine is one of the toxic elemental components of industrial emissions. Increased fluoride content in the atmosphere, soil or water negatively affects the growth and development of plants, as well as reducing resistance to various environmental stressors. An increase in ambient temperature causes a protective response in all organisms taking the form heat shock protein synthesis. The specific protein HSP101, which performs the function of protecting plant cells from heat damage, is also responsible for inducible thermotolerance, representing the ability of organisms to withstand the effects of severe heat shock that were previously exposed to mild heat stress, as a result of which heat shock proteins are induced. Heat shock proteins are involved in protecting not only against elevated temperatures, but also various other stress factors. In this work, the effect of sodium fluoride treatment on the viability of Arabidopsis thaliana cell culture, expression and synthesis of heat shock proteins was studied along with the role of heat shock protein HSP101 in providing resistance to fluoride. Sodium fluoride has been shown to significantly reduce the viability of A. thaliana cells by suppressing the activation of HSP101 gene expression with an increase in temperature. At the same time, the A. thaliana line, which has constitutive expression of the HSP101 gene, proved to be more resistant to the toxic effects of sodium fluoride.
Izvestiya Vuzov. Prikladnaya Khimiya i Biotekhnologiya. 2023;13(3):434-441
434-441
Study of the activity of antioxidant enzymes in somaclonal potato variants for use in selection for resistance to the PVS virus
Abstract
The article presents the results of a study into the activity of the antioxidant system of potatoes in response to infection with the PVS virus. The PVS virus is widespread in the Omsk region. The work set out to study the activity of antioxidant enzymes in somaclonal potato variants when infected with PVS virus to obtain valuable varietal characteristics for use in breeding selection. Potato varieties Yermak, Alena and the Khozyayushka were selected from the Omsk Agrarian Scientific Centre breeding lines as objects of research. Differences in resistance to viral infection in varieties of different susceptibility and obtained somaclones were studied using the example of changes in the activity of the isoenzyme composition of antioxidant enzymes. The results showed that somaclone EC1, which was derived from the susceptible Yermak variety, had two additional isoenzymes upon infection and an increase in isoperoxidase activity compared to the control. Although the number of isoperoxidases did not increase in the samples obtained from the stable HC94 and the moderately susceptible AC91 variety, an increase in their activity was noted. Activation occurs in infected plants of the additional 3rd isoforms of catalase compared to the control – 1 isoform, while the 4th isoform of catalase was detected in the EC1 somaclonal sample. When studying the superoxide dismutase spectra, the control group showed the activity of Mp-SOD and Fe-SOD, while two forms of the enzyme were identified in the HC94, AC91 and EC1 somaclonal samples: Feand Cu/Zn-SOD. These forms play a significant role in the neutralisation of the superoxide radical.
Izvestiya Vuzov. Prikladnaya Khimiya i Biotekhnologiya. 2023;13(3):442-453
442-453
Brief communication
Preparation of mcl-polyhydroxyalkanoate nanoparticles stabilized by the Tween 80 nonionic surfactant
Abstract
Nanoparticles based on biodegradable polymers find numerous applications in medicine as substances for intracellular drug delivery. Biosynthetically produced poly-3-hydroxyalkanoates (P3HAs) are among the most promising polymers of a lipid nature. In particular, polyhydroxybutyrate and polyhydroxyvalerate (scl-poly-3-hydroxyalkanoates) are widely used compounds, which are soluble only in organochlorine solvents. The use of organochlorine solvents faces several obstacles, since such chemicals may exhibit carcinogenic effects on the human body. However, the P3Has compounds consisting of hydroxybutyric acid residues with 6–14 carbon atoms in the main chain (mcl-poly-3-hydroxyalkanoates) are soluble not only in CHCl3 or CH2Cl2 but also in paraffins. These hydrocarbons, such as n-hexane, can be easily separated from aqueous solutions and are not known to exhibit high cytotoxicity. Consequently, the application of mcl-poly-3-hydroxyalkanoates can prevent the contamination of prepared dosage forms with organochlorine compounds. To this end, a methodology for the synthesis of mcl-P3HA nanoparticles stabilized with the Tween 80 nonionic surfactant was proposed. The ratio between the concentration of P3HA and the detergent was optimized. The present study revealed that the obtained particles have an average size of 200±90 nm and a zeta potential of -17±5 mV. Upon investigating the stability of the particle solution at 4 °C, it was found that the nanoparticles did not alter their size and zeta potential for 90 days. The fluorescence microscopy method showed that they could be delivered into BHK-21 cells within 2 h. In addition, the nanoparticles synthesized had no toxic effect on BHK-21 cells at a concentration of up to 200 μg/mL.
Izvestiya Vuzov. Prikladnaya Khimiya i Biotekhnologiya. 2023;13(3):454-460
454-460