Molecular-mass distribution of humus acids of taiga soils

Purpose of the study: to reveal the influence of hydromorphism and agricultural use on the molecular-mass distribution (MMD) of humic (HAs) and fulvic acids (FAs) isolated from the soils of the European northeast of Russia. To assess the influence of the acidity of the medium on the MWD of FAs. Place and time of the event. The studies were carried out on the territory of the middle taiga (Maksimovsky station of the Institute of Biology of the Federal Research Center of the KSC UB RAS, located 8 km west of the city of Syktyvkar and the field of the Syktyvkar state farm, 5 km south-west of Syktyvkar, on the watershed of the Sysola and Vazhel-yu rivers) and northern taiga (3 km west of the Troitsko-Pechorsk station). The objects of the study were humic substances isolated from typical podzolic (Eutric Albic Retisol (Loamic)), gleypodzolic (Eutric Albic Stagnic Retisol (Loamic)), peaty-podzolic surface-gleyed (Eutric Albic Stagnic Histic) Retisol (Loamic Eutric Albic Retisol (Loamic)) soils. The soil sampling period is from 1 to 30 August 2014. Methodology. Quantitative analysis of the MMD of HA and FA preparations was performed using liquid size exclusion chromatography (gel chromatography) on Sephadex G-25 and G-100 gels with continuous automatic registration of the optical density of the eluate (λ = 280 nm) in a quartz flow cell, K 9 × 60 cm column (Pharmacia, Sweden). Distilled water, 0.05 M NaOH solution, and Tris-HCl buffer with pH = 8.2 were used as the eluent. Main results. Studies of the MMD of humic substances have been carried out. It was found that HAs contain three fractions with different molecular weights: ≥ 150 kDa, 73–80 kDa, and 13–23 kDa; FAs – two fractions: ≥ 5 kDa, 1–2 kDa. The low molecular weight of FAs, together with a large amount of oxygen-containing functional groups, contributes to their better solubility and migration ability in soils. The HAs of automorphic soils are characterized by a high content of low molecular weight fractions, and the proportion of the high molecular weight fraction in the HAs of the litter is 1.5–2.0 times higher than in the HAs of the podzolic horizon, which may be due to the migration of the low molecular weight fraction down the profile. The high proportion of the acidic low molecular weight fraction in the podzolic horizon promotes the decomposition of soil minerals and their leaching into the illuvial horizon. The influence of agricultural use of soils on the fractional composition of humic compounds is estimated. A sharp increase in the share of the high molecular weight fraction in the preparations of HAs of arable podzolic soil by 2–4 times compared with the HAs of virgin podzolic soils was noted, which is due to the cultivation of the arable horizon, the nature of the incoming plant residues and the increased microbiological activity of the developed soils. The effect of acidity of the medium on the character of chromatograms of FA preparations isolated from the main types of soils of the Komi Republic was studied. It has been shown that in the region of high pH values of the eluent 9–13, the absence of fractionation is associated with the association of FAs, a change in their conformation, and the effect of “over-exclusion”. Elution with distilled water (pH = 6.5) allows the separation of FAs into two fractions with molecular weights ≥ 5 kDa and 1–2 kDa.

KINETIC PARAMETERS OF THE LIQID-PHASE FISCHER-TROPSCH SYNTHESIS IN THE PRESENCE OF Ru-CONTAINING CATALYSTS

Синтез Фишера-Тропша все больше привлекает внимание ученых, так как позволяет получать широкий спектр продуктов, на выход и молекулярно-массовое распределение которых оказывает влияние как катализатор, так и условия проведения процесса. В данной работе было изучено влияние на скорость и выход целевых продуктов - жидких углеводородов таких параметров процесса, как температура, состав синтез-газа, нагрузка на катализатор. На основании полученных зависимостей были найдены основные макрокинетические параметры - энергия активации и порядок реакции синтеза Фишера-Тропша. The Fischer-Tropsch synthesis is increasingly attracting the attention of scientists, since it allows a wide range of products to be obtained. The yield and molecular mass distribution of the products strongly depend on both the catalyst and the process conditions. In this work, the influence of such parameters as temperature, synthesis gas composition, the catalyst loading on the process rate and yield of the target products was studied. Based on the obtained dependencies, the main macrokinetic parameters were found -the activation energy and the reaction order of the Fischer-Tropsch synthesis.

Physicochemical Properties and Antioxidant Activity of Pumpkin Polysaccharide (Cucurbita moschata Duchesne ex Poiret) Modified by Subcritical Water

In this paper, subcritical water (SCW) was applied to modify pumpkin (Cucurbita moschata Duchesne ex Poiret) polysaccharides, and the properties and antioxidant activity of pumpkin polysaccharides were investigated. SCW treatments at varying temperature led to changes in the rheological and emulsifying properties of pumpkin polysaccharides. SCW treatments efficiently degraded pumpkin polysaccharides and changed the molecular weight distribution. Decreases in intrinsic viscosity, viscosity-average molecular weight, and apparent viscosity were also observed, while the activation energy and flow behavior indices increased. The temperature of SCW treatment has a great influence on the linear viscoelastic properties and antioxidant activity of pumpkin polysaccharides. Pumpkin polysaccharides solution treated by SCW at 150 °C exhibited the highest emulsifying activity and antioxidant activity, which was probably due to a broader molecular mass distribution and more reducing ends exposed after treatment. Scanning electron microscopy showed that SCW treatment changed the microstructure of pumpkin polysaccharides, resulting in the exposure of bigger surface area. Our results suggest that SCW treatment is an effective approach to modify pumpkin polysaccharides to achieve improved solution properties and antioxidant activity.

THE EFFECTIVENESS OF A COMPREHENSIVE STUDY OF COPOLYMERS EXEMPLIFIED BY COMMERCIAL NITRIL-BUTADIENE RUBBERS

Commercial nitril-butadiene rubbers were comprehensively studied by GPC, DSC, TGA, phase contrast microscopy and surface free energy determination via Owens-Wendt-Rabel-Kiellble method. Specific features were found for molecular mass distribution, phase transitions in negative and positive temperature intervals, the character of supramolecular assembly and microblock distribution of functional groups in BNKS-18AN and BNKS-18AMN rubber brands. A set of differences in initial rubbers macromolecular characteristics was shown, as well as the evolution of the latter during mechanical activaction of BNKS-18AN and BNKS-18AMN rubber brands

Analysis of glycidyl nitrate polymerization reaction

Poly(glycidyl nitrate) (PGN) is a high-energetic polymer whose properties are determined by the presence of an –ONO2 explosophoric group. PGN can be obtained by polymerization of glycidyl nitrate (GN) monomers. The preferred polymerization route is via the activated monomer mechanism, due to its two main advantages: narrow molecular mass distribution of the obtained polymer and ability to control the heat generated during the reaction. The study allowed the GN monomer to be obtained as a product of nitration of epichlorohydrin. A series of GN polymerization reactions was conducted under different conditions (temperature, time and reactant amounts). The analysis showed that the lower the catalyst to initiator ratio, the higher the molecular mass of the obtained polymer (PGN). A temperature between 0-10 °C is the optimum temperature for GN polymerization. The longer the GN polymerization time the higher the molecular mass of the PGN. The GN polymerization reaction was scaled up without affecting the molecular mass or other properties of the obtained polymers. The following tests were carried out to determine the basic properties of PGN: GPC, 1H NMR, FTIR, DSC, TG, calorific value, viscosity, sensitivity to friction and impact.

The Hydrocarbon Genesis of pre-Jurassic Complex of Khanty-Mansiyskoe Oil Field

The origin of hydrocarbon deposits in Jurassic and pre-Jurassic complexes of the Khanty-Mansiysk area, located within the Frolov depression, in the local compression zone of the West Siberian plate — the suture zone, is established. The core and crude oil of Jurassic and pre-Jurassic complexes from prospecting wells of the Khanty-Mansiyskoe field is studied. The content and molecular mass distribution of hydrocarbons, including n-alkanes, n-alkylbenzenes, naphthalene’s and phenanthrenes, is determined in bitumen of rocks and oils by chromatography-mass spectrometry. Lithological and petrographic characteristics of rocks is determined by optical microscopy. For oil deposits of the pre-Jurassic complex “source of hydrocarbons” is not reliably established, the parent rocks were not clearly identified in this research. In the lower horizons of the Jurassic section, there is a layer of highly permeable gritstone of the Gorely formation, in which organic matter is localized, presumably making the main contribution to the hydrocarbon deposits of the lower Jurassic and pre-Jurassic complexes. As a possible “source of Paleozoic oil”, it is proposed to collect hydrocarbons from scattered organic matter of Paleozoic rocks at a significant depth (not covered by core drilling) in the areas of tectonic block crushing of foundation.

Dromedary Milk Protein Hydrolysates Show Enhanced Antioxidant and Functional Properties

Research background. Milk protein hydrolysates have received particular attention due to their health-promoting effects. Dromedary milk differs from the milk of other dairy animals in the composition and structure of its protein components, which give it unique properties. The bioactivity and functionality of whole dromedary milk proteins and their enzymatic hydrolysates have not received much attention, hence this study aims to investigate the effect of enzymatic hydrolysis of dromedary milk proteins on their antioxidant activities and functional properties. Experimental approach. Dromedary milk proteins were treated using four proteolytic enzymes (pepsin, trypsin, α-chymotrypsin and papain) and two mixtures of enzymes (pancreatin and pronase). The degree of hydrolysis was measured to verify the hydrolysis of the proteins. The sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) and gel filtration chromatography served to determine the molecular mass distribution of the hydrolysates while reversed phase-high performance liquid chromatography (RP-HPLC) was conducted to explore their hydrophobicity. The antioxidant activities were evaluated using various in vitro tests, including 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid (ABTS) radical scavenging capacities, iron(III) reducing ability and chelating activity. Besides, functional properties such as solubility, foaming and emulsification were assessed. Results and conclusions. Dromedary milk protein hydrolysates exhibited different degrees of hydrolysis ranging from 17.69 to 41.86 %. Apart from that, the hydrolysates showed different electrophoretic patterns, molecular mass distribution and RP-HPLC profiles demonstrating the heterogeneity of the resulting peptides in terms of molecular mass and polarity. The hydrolysates displayed significantly higher antioxidant capacities than the undigested proteins at all the tested concentrations. Iron(II) chelating activity was the most improved assay after proteolysis and the hydrolysate generated with pancreatin had the highest chelating power. Dromedary milk protein hydrolysates possessed good solubility (>89 %). Further, foaming and emulsifying properties of dromedary milk proteins were enhanced after their proteolysis. These interfacial properties were influenced by the enzymes employed during proteolysis. Novelty and scientific contribution. Enzymatic hydrolysis of dromedary milk proteins is an effective tool to obtain protein hydrolysates with great antioxidant and functional properties. These results suggest that dromedary milk protein hydrolysates could be used as a natural source of antioxidant peptides to formulate functional foods and nutraceuticals.

Depolymerization of Pine Ethanol Lignin in the Medium of Supercritical Ethanol in the Presence of Catalysts NiCu/SiO₂ and NiCuMo/SiO₂

The regularities of thermocatalytic transformation of pine ethanol lignin in supercritical ethanol in the presence of catalysts NiCu/SiO₂ and NiCuMo/SiO2 in the temperature range 250–400 °C were established. The composition and structure of ethanol lignin, liquid and solid products of its conversion were studied by methods of elemental analysis and gel-permeating chromatography (GPC). The composition of gaseous products – by method of gas chromatography. At the process temperature of 250 °C the catalysts do not have a significant effect on conversion of ethanol lignin. The maximal yield of liquid products (83.5 wt. %) was obtained at temperature 300 °C in the presence of catalyst NiCuMo/SiO₂ containing 8.8 wt. % of molybdenum. At temperature 350 °C NiCu/SiO₂ and NiCuMo/SiO2 catalysts contribute to the almost complete conversion of ethanol lignin into liquid and gaseous products, and the yield of solid products does not exceed 1 wt. %. In liquid products of catalytic conversion there is a decrease in the atomic ratio of O/C and the increase of H/C atomic ratio as compared to initial ethanol lignin due to catalytic intensification of reactions of deoxygenation and hydrogenation of lignin and products of its depolymerization. According to GPC data on the curves of molecular mass distribution (MMD) of liquid products of thermocatalytic conversion of ethanol lignin at 300 °C there are peaks with highs at 160 and 380 Da, probably related to guiacyle monomers and dimmers, respectively. From the comparison of MMD of liquid products obtained by ethanol lignin depolymerization at 300 °C over catalysts NiCu/SiO₂ and NiCuMo/SiO₂ it follows, that the introduction of molybdenum in the catalyst promotes the formation of monomeric guaiacyl products

D,L-polylactide degradation in biological media: experiment and model

The processes of changes in the surface morphology and internal structure, as well as the molecular mass distribution of amorphous D, L polylactides during their hydrolytic degradation in the presence of extra-germinal mesenchymal stem cells (MSCs) (ratschwart jelly umbilical cord) of the rat and their metabolic products have been studied. It was shown that the degradation of initially monolithic polymer samples in culture and conditioned media occurs almost identically. However, in a culture medium containing MSCs, this process is much more intense. This effect can be interpreted in terms of the influence of enzymes secreted by living cells, which diffuse from the surface into the polymer sample and accelerate its hydrolysis, entering into a catalytic reaction with the ether bonds of polylactide molecules. A mathematical model has been developed and verified that takes into account both non-catalytic and catalytic channels of hydrolysis, changes in the porosity of the polymer sample, diffusion of short-length oligomers, and adequately interprets the experimental results.