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Том 42, № 7 (2016)

Article

Investigation of mechanical properties, morphology, and biodegradability of compositions based on polylactide and polysaccharides

Rogovina S., Aleksanyan K., Gorenberg A., Deryabina Y., Isakova E., Prut E., Berlin A.

Аннотация

The blends of polylactide with ethyl cellulose and chitosan are obtained in a Brabender mixer under conditions of high temperature shear deformation at different initial ratios of the reagents. The investigation of physicomechanical properties of the compositions has shown that the systems have high rigidity. Polyethylene glycol (PEG) and high-molecular-weight polyolefin polydecene have been added to the compositions in order to improve their elasticity. It has turned out that polydecene scarcely affects the mechanical characteristics, while PEG leads to a noticeable increase in elongation at break. Biodegradability of the compositions is investigated by the mass loss of samples after holding in soil, fungus resistance tests, and the analysis of the film morphology by scanning electron microscopy after holding in soil. It is found that the introduction of the third component (PEG) leads to an increase in biodegradability of the compositions.

Russian Journal of Bioorganic Chemistry. 2016;42(7):685-693
pages 685-693 views

Transformation of wheat straw polysaccharides under dynamic conditions of subcritical autohydrolysis

Evstafev S., Chechikova E.

Аннотация

Transformation of wheat straw polysaccharides under dynamic conditions of subcritical autohydrolysis has been examined at a pressure of 30 MPa in a temperature range of 150—290°C. The dependence of the yield of gaseous, liquid, and solid products on the process temperature has been studied. The formation of liquid products occurs mainly due to the hydrolysis of pentosans and partially of cellulose in a range of 150–200°C. The main components of liquid products are oligo- and monosaccharides. Xylose and arabinose comprise more than 65% of monosaccharides. A temperature rise in a range of 200–290°C is accompanied by a decrease in medium pH, cellulose hydrolysis, and intensive gasification. Glucose predominates in monosaccharides of liquid products isolated at 270°C; a portion of pentoses does not exceed 25% of the total of monosaccharides. The maximal yield of sugars is observed at 200°C and then decreases from 29.6 to 5.3% per straw oven-dry weight at 270°C. A decrease in reactivity of straw cellulose treated at 200°C to enzymatic hydrolysis has been found.

Russian Journal of Bioorganic Chemistry. 2016;42(7):700-706
pages 700-706 views

Oligolignans in the wood of Picea obovata Ledeb.

Fedorova T., Fedorov S., Babkin V.

Аннотация

We studied the chemical composition of the phenolic complex and the structure of oligomeric lignans in Siberian spruce (Picea obovata Ledeb.). We used the wood of Siberian spruce collected near the city of Irkutsk. The extractives were isolated from ground wood (particle size: 10–15 mm; humidity: 5.9%) by three-stage acetone extraction. The extract was separated by consecutive treatment with the solvents with increasing polarity: hexane, ethyl acetate and n-butanol. The main amount of phenolic compounds (lignans) was concentrated in the ethyl acetate fraction and it was 0.7% in absolutely dry wood (adw).

The ethyl acetate fraction of spruce wood extract was separated by silica gel column; a chloroform-acetone mixture was used as the eluent (the concentration of acetone in the mixture was increased from 0 to 100%). Monomeric lignans (~60–65% of the ethyl acetate fraction of spruce wood extract), oligomeric lignans (~20–25%), and polymer lignans (~12–15%) were isolated.

We also obtained 13C nuclear magnetic resonance (NMR) spectra for the main monomeric, oligomeric and polymeric lignan compounds of phenolic complexes. It was found that oligomeric and polymeric fractions contain monomeric lignan units with the butyrolactone cycle, primarily, the fragments with hydroxymatairesinol structure. Oligomeric lignans contain the fragments with a pinoresinol and lariciresinol structure. All the monomeric structural units are characterized by the guaiacyl substitution type of the aromatic cycles.

A preliminary study has been performed on the antiviral and antioxidant activity of the ethyl acetate fraction of acetone extract of Siberian spruce wood. It was found that the lignan complex is active against Coxsackie B4 virus in cell culture and in the pancreatitis model in white mice, reducing the activity of enteroviruses in the cell culture approximately 100 times. The antioxidant activity rate of polyphenol complex of Siberian spruce wood is comparable to that of a known antioxidant dihydroquercetin.

Russian Journal of Bioorganic Chemistry. 2016;42(7):712-715
pages 712-715 views

A mass spectrometry study of the self-association of glycyrrhetinic acid molecules

Borisenko S., Lekar’ A., Vetrova E., Filonova O., Borisenko N.

Аннотация

The formation of self-associates of glycyrrhetinic acid (GLA), an aglycone of glycyrrhizic acid (GA), has been studied by electrospray ionization mass spectrometry. It has been shown for the first time that, analogously to triterpene saponins having free carboxyl groups, GLA stereoisomers can form self-associates. The capacity of GLA to form self-associates has been confirmed by the mass spectrometry data. It has been found that the ionization of GLA self-associates with the formation of an anion proceeds rather weakly. The ionization of GLA in the positive ion mode goes on effectively and makes it possible to record multidimensional structures of one to eight 18α-GLA molecules and from one to nine 18β-GLA molecules. The structure of GLA associates and their stability are demonstrated most comprehensively in positive ion mass spectra. As a whole, the sets and intensity of peaks for 18α- and 18β-GLA correlate well. The results of the mass spectrometry study show the capacity of 18α- and 18β-GLA stereoisomers to form self-associates, which indicates a high potentiality of GLA in providing noncovalent interactions during the formation of supramolecular complexes. Similarly to the saponins of licorice and ivy, GLA stereoisomers may form a potential basis for the synthesis of a new generation of noncovalent molecular complexes and novel highly effective medicinal substances owing to a possible improvement in bioaccessibility and possible synergistic effects.

Russian Journal of Bioorganic Chemistry. 2016;42(7):716-720
pages 716-720 views

Molecular complexes of ivy triterpene glycosides with β-cyclodextrin

Yakovishin L.

Аннотация

Molecular complexes of triterpene glycosides such as α-hederin (hederagenin 3-O-α-L-rhamnopyranosyl-(1 → 2)-O-α-L-arabinopyranoside) and hederasaponin C (hederagenin 3-O-α-L-rhamnopyranosyl-(1 → 2)-O-α-L-arabinopyranosyl-28-O-α-L-rhamnopyranosyl-(1 → 4)-O-β-D-glucopyranosyl-(1 → 6)-O-β-D-glucopyranoside) with β-cyclodextrin were synthesized. The complex formation was studied by FTIR spectroscopy. Toxic properties of the molecular complexes were examined.

Russian Journal of Bioorganic Chemistry. 2016;42(7):721-725
pages 721-725 views

Composition of the essential oil from the lemon balm growing in the neighborhood of Krasnoyarsk as indicated by gas chromatography–mass spectrometry data

Efremov A., Zykova I., Gorbachev A.

Аннотация

Essential oil has been isolated from the above-ground part of the lemon balm growing in the neighborhood of Krasnoyarsk by the method of exhaustive water and steam distillation. Forty seven components, each with a content of more than 0.1% of whole oil, have been identified by GC-MS. The main oil components are citronellol (36.71%) and geraniol (27.20%). The oil also contains ten components with a content of more than 1% of the sum of all oil components: benzyl alcohol (1.67%), linalool (1.75%), citronellal (1.44%), neral (3.33%), geranial (4.39%), caryophyllene (3.73%), caryophyllene oxide (1.40%), dibutyl phthalate (1.36%), butylisobutyl ester of phthalic acid (2.45%), and phytol (2.55%). The composition of lemon balm oils from different regions of the world has been compared.

Russian Journal of Bioorganic Chemistry. 2016;42(7):726-729
pages 726-729 views

Composition of essential oil of Artemisia scoparia Waldst. et Kit. from Buryatia and Mongolia

Zhigzhitzhapova S., Randalova T., Radnaeva L.

Аннотация

Essential oil from the epigeal portion of Artemisia scoparia Waldst. et Kit. collected in different regions of Buryatia and Mongolia has been isolated using steam distillation. The yield of essential oil from the stems and leaves of A. scoparia collected in different regions of Buryatia and in the Selenga aymag of Mongolia ranged from 0.06 to 0.40%, that is, the variation was rather high. The composition of the oil was analyzed using chromatography with mass spectrometric detection on a gas chromatography device Agilent Packard HP 6890 N with a quadrupole mass spectrometric detector HP MSD 5973. The total number of compounds detected exceeded 100. The major components of Artemisia scoparia oil were the following: p-cymene (0.6–15.2%), limonene (0.1–6.3%), α-pinene (0.2–10.1%), β-pinene (0.4–8.9%), trans-β-ocimene (0.3–5.4%), caryophyllene (4.6–13.8%), germacrene D (11.5–40.3%), spathulenol (4.0–11.7%), and caryophyllene oxide (4.3–15.6%). Several chemotypes of essential oil from A. scoparia were identified according to the nature of the major components: 1) oil that contained acetylene hydrocarbons (from plants collected in Gilan, Mazandaran, Kashan, and Tigran provinces of Iran, Tajikistan, and the European part of the CIS); 2) oil that contained monoterpenes and aromatic compounds (from plants collected in the Khorasan province of Iran, India, and South Korea); and 3) oil that contained monoterpenes or aromatic and sesquiterpene compounds (from plants collected in Kazakhstan and Mongolia). The major components of A. scoparia essential oil obtained from Buryatian plants belonged to the classes of mono- and sesquiterpene compounds, and thus the oil can be assigned to the third chemotype characteristic of A. scoparia from geographically close regions.

Russian Journal of Bioorganic Chemistry. 2016;42(7):730-734
pages 730-734 views

Comparative study of antioxidant properties of extracts of various Aloe species

Sazhina N., Lapshin P., Zagoskina N., Misin V.

Аннотация

Nowadays, a search for sources of the most biologically active antioxidant compounds among various herbs is an urgent problem. In this connection, several succulent plants from the Aloe genus are of special interest, because their preparations are widely used in domestic medicine. In this study, we measured the antioxidant activity (AOA) of an alcoholic extract of leaves of 15 Aloe species by amperometric and chemiluminescent methods and performed a comparative analysis of the results. We observed a considerable difference between the AOA values for the several Aloe species and explained this fact. The most active antioxidant among the samples proved to be the A. pillansii representative of the Aloe genus. Both methods demonstrated that the extracts from leaves of this Aloe species exhibited the high AOA. The A. broomii and A. spinosissima also had rather high AOA along with the A. pillansii and A. arborescens. The newly discovered Aloe species could be as promising a source of biologically active compounds as the traditionally used A. arborescens and A. vera.

Russian Journal of Bioorganic Chemistry. 2016;42(7):735-740
pages 735-740 views

Thermal transformation of betulin by alkaline activation

Mikova N., Chesnokov N., Mazurova E., Pavlenko N., Ivanchenko N.

Аннотация

Carbonization of betulin (betulinol) as an individual carbon precursor was studied in the temperature range of 400–800°C in the presence of KOH. Differential thermal analysis and IR spectroscopy were used to determine the influence of KOH on major structural changes and the chemical composition of betulin, which occur at 400–500°C. It was shown by scanning electron microscopy and BET analysis that KOH promoted the formation of a developed specific surface (SBET 1350–2100 m2/g) at temperatures of 600–800°C and had the greatest influence on the textural and adsorption properties of the resulting porous carbon adsorbents. It has been found that the formation of microporous carbon materials with a pore size of 1.92 nm and a specific micropore surface area of 1275 m2/g is possible upon the activation of betulin with KOH at 800°C. Betulin may be proposed to control the porosity of the carbon carriers derived from birch wood.

Russian Journal of Bioorganic Chemistry. 2016;42(7):741-747
pages 741-747 views

Biocatalytic properties of immobilized inulinase

Shkutina I., Stoyanova O., Selemenev V.

Аннотация

A heterogeneous biocatalyst based on inulinase immobilized on a nonionic sorbent of Stirosorb series was proposed. Thermal and acid inactivation of free and immobilized inulinase was examined and the corresponding inactivation constants were calculated. An increase in the thermal stability of the immobilized enzyme in comparison to the free one was found. The possibility of using the immobilized enzyme in the hydrolysis of inulin for ten cycles was determined.

Russian Journal of Bioorganic Chemistry. 2016;42(7):748-751
pages 748-751 views

Kinetic determination of vitamin E in wheat germ oil

Sizova N.

Аннотация

The content of vitamin E in wheat germ oil produced by different manufacturers was determined with a microcalorimetry approach. The maximum amount of tocopherols was shown to be contained in the wheat germ oil produced by mechanical processing of the initial raw material according to Prof. A.B. Vishnyakov’s sparing technology. Eight samples of wheat germ oil produced in different processing cycles by OOO SibTar in the years 2011–2015 were analyzed. The synergistic oil components provided the high content of antioxidants, corresponding to the total content of tocopherols ranging from 240 to 420 mg%, which exceeds the reference data. The key elements for obtaining oil with a high content of vitamins are the use of high quality raw materials and pressing without heating or using any solvents. The content of tocopherols for oils produced from crops of different years was found to vary by 40%, depending mostly on growth and storage conditions of the grain. The content of tocopherols in an oil kind could serve as the oil quality criterion. For example, the values of vitamin E content obtained for two of the wheat germ oil samples tested were three times lower than the reference values, which indicates that these oil samples had been diluted with others kinds of oil.

Russian Journal of Bioorganic Chemistry. 2016;42(7):752-755
pages 752-755 views

Elaboration and validation of methods for quantitative analysis of phenolic compounds and flavonoids in the extracts of higher fungi

Protsenko M., Kostina N.

Аннотация

Simple express methods for the quantitative evaluation of phenolic compounds and flavonoids in the extracts of basidiomycetes and plants were developed using ethanol extracts of the Fomes fomentarius xylotrophic fungus as a model system. The analysis of phenolic compounds was based on the photocolorimetric Folin–Ciocalteu method. The spectrophotometric method based on the reaction of complex formation with aluminum chloride was chosen for the analysis of flavonoids. The composition of the reactants and their concentrations in the reaction mixtures were optimized for both techniques. The advantages of the developed techniques were the following: the simplicity, speed, the use of commonly used laboratory equipment, and the small volumes of the test samples and reagents. The proposed methods allow for serial analyses of up to four dozen samples. It was found that the decrease of the volume of the studied sample by factors of 5–10 did not reduce the sensitivity of the techniques in comparison with the classic versions of the methods. The proposed methods were examined for linearity, accuracy, repeatability, and convergence. The validation showed that the methods meet the eligibility criteria. The proposed methods for the quantitative analysis of phenolic compounds and flavonoids can be recommended for the characterization of fungi and plant extracts of both natural and biotechnological origin.

Russian Journal of Bioorganic Chemistry. 2016;42(7):756-763
pages 756-763 views

Chemical composition and biological action of rowanberry extract

Fomenko S., Kushnerova N., Sprygin V., Drugova E., Momot T.

Аннотация

The object of this study was the extract from the dried pomace of the Amur rowanberry (Sorbus amurensis Koehne) after the juice separation. The content of total polyphenols, lipid composition, and antiradical activity of the extract were studied. The total content of polyphenols proved to be 80 ± 2,5 mg-equivalents of gallic acid per 100 mL of the extract, suggesting the high level of its antiradical activity (29.73 ± 0.23 mmolequivalents of trolox per liter). The lipid part of the extract included three phospholipid fractions and six fractions of neutral lipids. Their content was found to be 13.4 ± 0.14 mg of total lipids/mL. These results pointed to a high biological activity of the extract which could be considered as a promising object for further experimental studies. The Amur rowanberry extract was shown to exhibit a pronounced antioxidant and hepatoprotective activity on the laboratory model of the carbon-tetrachloride-induced hepatitis in rats with endogastric administration at a dose of 100 mg of total polyphenols per kg of body weight. Administration of the extract resulted in a decrease in the content of total lipids, specific liver weight, and the activity of alanine aminotransferase. The level of the reduced glutathione and the activity of antioxidant and lysosomal enzymes were also normalized. The rowanberry extract seemed to be a promising source for the creation of biologically active food supplements with high antioxidant and antiradical activity.

Russian Journal of Bioorganic Chemistry. 2016;42(7):764-769
pages 764-769 views

Polyphenolic compounds of a new biologically active extract from immortelle sandy flowers (Helichrysum arenarium (L.) Moench.)

Grinev V., Shirokov A., Navolokin N., Polukonova N., Kurchatova M., Durnova N., Bucharskaya A., Maslyakova G.

Аннотация

The chemical composition of a new bioactive extract from immortelle sandy (Helichrysum arenarium (L.) Moench.) was investigated. Naringin, its soluble aggregate, prunin, quercetin, apigenin, naringenin, apigenin 5-O-glucoside, and isosalipurposide were found among the flavonoids. The tested immortelle sandy extract was shown to contain known dimers, trimers, or more complex aggregates. The compounds had similar spectral but substantially different chromatographic characteristics, which can be used for their identification based on the corresponding data on flavonoids glycosylated at different positions and/or carbohydrates of various complexities, which are also characterized by similar absorption spectra and different retention times. It was found by molecular absorption spectroscopy that the immortelle extract contained 73.48 mg of flavonoids relative to rutin or 17.94 mg relative to quercetin per 1 g of dry extract weight, which corresponded to 20.99 and 5.13%, respectively. The immortelle extract obtained by the method proposed displayed antitumor activity against the transplanted sarcoma 45 and had a beneficial effect on animals in general.

Russian Journal of Bioorganic Chemistry. 2016;42(7):770-776
pages 770-776 views

Features of the mechanical treatment of rice husk for the performance of the solid-phase reaction of silicon dioxide with polyphenols

Shapolova E., Lomovskij O.

Аннотация

The distinguishing features of rice husk are high strength properties, chemical stability, high ash content, and low nutritional value, which are determined by the composition and structure of this type of raw material. The goal of the study was to determine optimal methods of mechanical treatment for the performance of a solid-phase reaction of silicon dioxide from rice husk with polyphenol compounds. Different regimes of the treatment of plant raw material have been compared. It has been shown that, for the solid-phase reaction of silicon dioxide from plant raw material with polyphenol compounds to occur, both the destruction of the supramolecular complex of silicon dioxide with the lignocellulose matrix, which is accomplished by fine grinding, and the plastic deformation of the silicon dioxide phase with the formation of reaction centers are necessary. These operations can be brought about using grinders with the attrition and shear modes of operation, including roller mills. It is preferable that silicon dioxide is in the composition of plant raw material since the reaction between silicon dioxide and polyphenols with the formation of surface complexes requires the presence of silanol groups. If silicon dioxide is derived from rice husk by conventional methods, most hydroxyl groups are eliminated, which significantly decreases the reactivity.

Russian Journal of Bioorganic Chemistry. 2016;42(7):777-782
pages 777-782 views

Plant Biopolymers

Degradation of polysaccharides and lignin in wood ozonation

Mamleeva N., Autlov S., Bazarnova N., Lunin V.

Аннотация

Ozonation has been considered as a method for the pretreatment of plant biomass to obtain cellulose and monosaccharides. Ozone consumption by aspen wood with various moisture contents has been investigated. We have considered the gradual transformation of the substrate: wood to ozonated wood to cellulose-containing product (CP) to holocelluloze (HC) and to cellulose. Yields of ozonated wood (OW), the (CP), water-soluble ozonation products, HC, and cellulose have been determined. The lignin content in the CP has been estimated. Both HC and cellulose samples have been studied by IR spectroscopy. The degree of polymerization and molecular mass distribution of cellulose obtained from ozonated wood have been determined. It has been shown that wood destruction by ozone is accompanied by degradation of lignin, hemicelluloses, and cellulose.

It has been found that physicochemical properties of cellulose obtained from ozonated wood can be regulated by the variation of the initial moisture content in the substrate. Both molecular ozone and radical species, which are generated in the course of ozone reactions with water present in the substrate structure, participate in wood destruction.

Russian Journal of Bioorganic Chemistry. 2016;42(7):694-699
pages 694-699 views

Investigation of physicochemical properties of arabinogalactan of different larch species

Babkin V., Neverova N., Medvedeva E., Fedorova T., Levchuk A.

Аннотация

Samples of arabinogalactan (AG) were isolated by aqueous extraction from wood of different larch species (Larix sibirica Ledeb., Larix gmelinii (Rupr.) Rupr., Larix cajanderi Mayr., and Larix olgensis var. Koreana) and studied by HPLC, IR spectroscopy, and quantitative 13C NMR spectroscopy. The wood of the studied larch species was shown to contain significant amount of arabinogalactan (10–17% of the a.d.w. mass) and could be a source of its industrial production. The studied AG samples had similar structural and molecular-mass characteristics. This fact could facilitate the product standardization during its industrial production both from the wood of a single larch species and from mixed raw materials.

Russian Journal of Bioorganic Chemistry. 2016;42(7):707-711
pages 707-711 views

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