CHEMICAL SCIENCES
The presence of water complexes and clusters in hydrolysis and hydration reactions implies complex multi-step processes involving various mechanisms. The concentration of neutral and charged complexes and clusters in the reaction mixture affects the rate and mechanism of hydrolysis. Therefore, the aim of this work was to calculate the concentrations of the complexes and clusters involved in gas -phase hydrolysis of thionyl chloride, as well as to establish the most probable reaction channels. Based on the thermodynamic data obtained by the B3LYP/6–311++G(2d,2p), MP2/aug-cc-pVTZ and G4 methods of quantum chemical modelling, the gas-phase concentrations of the complexes and clusters of water and thionyl chloride, as well as the hydrolysis products of the latter, were calculated. The structures of water complexes of composition (H2O)n (n = 1-5.8) were identified and optimised. Acyclic structures of the (H2O)4 and (H2O)5 complexes were identified in the gas phase having concentrations different from those calculated in cyclic complexes. Calculated concentrations of charged complexes and clusters (H+ )∙(H2O)n and (H2O)n·(OH-) Cl-(H2O)n, SOCl+(H2O)n, (SOCl2(H2O)n) - are negligible. Therefore, the assumption concerning the hydrolysis of formed or existing ionic particles in the gas phase inside water clusters can be excluded. Concentrations of SOCl2(H2O)n and HCl (H2O)n neutral clusters range from 1014 to 101 molecules/cm3 , depending on the number of water molecules in a cluster. SOCl2(H2O) and HCl(H2O) are characterised by the highest concentration. A calculation of SOCl2(H2O)n cluster concentrations was performed under the assumption that the concentration of thionyl chloride is equal to the concentration of saturated water vapour, which is quite possible near industrial facilities for the production of high-capacity current sources. The most probable channels for hydrolysis are presented by reactions of complexes and clusters having the highest concentrations. These reactions of (H2O)n and SOCl2(H2O)n neutral clusters are in a good agreement with the results of previous work.
In this article, a description of the photochemical degradation of phenol with TiO2 nanoparticles for the treatment of toxic substances in water basins is presented. Such research is of great relevance due to the discharge of wastewater into clean water basins resulting in a contamination of ecosystems with very ecological consequences. Due to the seemingly inevitable reduction in the world’s freshwater reservoirs, finding new methods for the high-level purification of contaminated waters so as to minimise the toxic substance content is of paramount importance. Composition and quantitative analysis of the photolysis solution was carried out using the gas chromatographic method. TiO2 nanopowders were prepared using the sol-gel method from titanium IV isopropoxide (TTIP), isopropyl alcohol and ammonium hydroxide precursors under normal conditions without any post-heat treatment for crystallisation. The nanocrystalline rutile-phase TiO2 powders were characterised by X-ray powder diffraction (XRD). The size of nanoparticles as confirmed by transmission electron microscopy (TEM) was about 10–20 nm, while the Brunauer–Emmett–Teller (BET) specific surface area of the rutile nanopowder was 159.6 m2/g. The photocatalytic performance of the synthesised nanopowders photochemical was observed to enhance degradation of the phenol solution under UV irradiation. The phenol degradation was quantitatively analysed using a 6890N GC-MSD gas chromatograph with an Agilent 5975 highperformance mass-selective detector. Degradation of phenol in the presence of TiO2 nanopowders yielded a rate of 99%.
This paper provides an overview of the features specific to the nuclear magnetic resonance (NMR) of paramagnetic molecules. These features can be attributed to the hyperfine or electronic coupling between unpaired electrons, which are localised on the coordinating ion, and resonant nuclei. That leads both to the paramagnetic broadening and to the paramagnetic shifts (contact and pseudo-contact ones) of resonance lines in the NMR spectra. A contact shift is observed when the probability of an unpaired electron location in the place of a resonant nucleus differs from zero. Therefore, these shifts constitute a source of information on the nature of the metal-ligand bond as well as on the ligand electronic structure. Pseudo-contact shifts characterise the spatial structure of the molecule, thus being important for solving various structural problems. This paper covers pioneering works describing the specifics of the NMR spectra transformed by adding paramagnetic complexes of iron-group elements on the example of cobalt and nickel complexes, as well as complexes of rare-earth elements on the example of europium. We present main features of the paramagnetic additives method, allowing resolution of difficulties associated with large paramagnetic broadening of resonance lines in high-resolution NMR spectra. Of iron-group elements, a paramagnetic ion Co2+ is shown to be an effective shift reagent. In some cases, a Ni2+ ion may also be used for this purpose. The paper covers conditions for recording the NMR spectra of samples containing paramagnetic additives; solvents used for this purpose; as well as temperature variations of the studied samples in the context of resonance signal detection.
The paper analyses complexation of thorium(IV) with 2,3,4-trihydroxy-4’-fluoroazobenzene. A complex is formed immediately after mixing the components. Their molar ratio (1:2) was established using the methods of Starik–Barbanel relative yield, equilibrium shift and isomolar series. The maximum light absorption of the complex is observed at 440 nm, with the molar absorption coefficient being equal to 1.80×104. In this work, we synthesised a new sorbent containing fragments of para-aminosalicylic acid. Identification of sorbents was carried out using IR spectroscopy. Sorption was studied in static and dynamic modes. The optimal conditions for concentration were investigated. The magnitude of the sorption and the degree of metal extraction was calculated from its residual concentration in the solution using a spectrophotometric method. Our results show that the maximum sorption is observed at pH = 4. In the course of preliminary kinetic experiments, it was found that the maximum sorption of cadmium is attained within 2 hours, remaining practically at the same level thereafter. The effect of the ionic strength of the solution was studied using the photometric method. Thorium(IV) was sorbed from solutions having an ionic strength of 0.1–1.4. It is shown that a significant decrease in the sorption of thorium(IV) occurs in solutions with an ionic strength of more than 0.2 M. The effect of metal concentration on sorption was also investigated. An isotherm of thorium sorption by the synthesised sorbent was constructed. An increased concentration of thorium(IV) in the solution leads to an increase in the amount of sorbed metal, with the maximum concentration being reached at 1856 mg/l. We also studied the effect of various acids (HClО4, H2SО4, HNО3, HCl) on the desorption of thorium(IV) from the sorbent: thorium(IV) was quantitatively desorbed by 2 M nitric acid. The degree of extraction of thorium ions (IV) under optimal conditions exceeds 95%. The study has revealed the possibility of using the matrix of a copolymer of maleic anhydride and styrene modified by para-aminosalicylic acid for sorption-photometric determination of thorium(IV). Following regeneration, this sorbent can be reused.
A comprehensive physico-chemical study of individual systems provides important experimental data, which can be further used both in basic and applied research. Thus, a number of systematic studies have revealed the formation of complex molybdates, which can be classified in terms of cationic composition. Many compounds belonging to this class are shown to possess valuable functional properties. In this work, we set out to generalise and complement the results obtained on phase formation in K2MoO4 – R2(MoO4)3 – Zr(MoO4)2 salt systems (R = Al, Cr, Fe, In, Sc, Y, Bi, La –Lu) dependent on the nature of the molybdates of trivalent elements. In addition, we aim to determine synthesis conditions and to characterise properties of these triple molybdates. To this end, methods of X-ray phase analysis, differential scanning calorimetry, electron microscopy and impedance spectroscopy were used. Interaction in ternary salt systems K2MoO4 – R2(MoO4)3 – Zr(MoO4)2 (R = Al, Cr, Fe, In, Sc, Y, Bi, La – Lu) was studied at subsolidus temperatures across the 723–873 K range. Transformation of phase diagrams was demonstrated; the systems were divided into ten triangulation types. The identified new triple molybdates of the K5RZr(MoO4)6 (R = Al, Cr, Fe, In, Sc, Y, Bi, Dy - Lu) composition were obtained via solid-phase synthesis at temperatures of 723–773 K. Their crystallographic and thermal properties were determined. Molybdates of the K5RZr(MoO4)6 composition are established to crystallize in a hexagonal crystal system and a trigonal crystal system under R = Al, Cr, Fe, In, Sc (space group P63, Z = 2) and under R = Dy - Lu, Y, Bi (space group R`3c, Z = 6), respectively. The electrical conductivity of K5RZr(MoO4)6 (R = Fe, In, Er) was studied using the method of impedance spectroscopy across the temperature range of 300–900 K. It is also demonstrated that the conductivity values of this compound amount to 10-2 S/cm at 700–850 K.
PHYSICOCHEMICAL BIOLOGY
The article presents the results of research into the biotechnological processing of collagencontaining raw materials (bovine rumina) to create functional foods. The patterns of biotransformation of collagen-containing raw materials by activated cultures of probiotic microorganisms (Bifidobacterium longum B379 M, Propionibacterium shermanii KM 186 and Lactobacillus helveticus Н17-18) have been studied and theoretically substantiated. It is noted that bovine rumina, following preliminary heat treatment, comprise a good nutrient medium for the development of probiotic cultures. It was revealed that low-molecular compounds formed during the heat treatment of rumina possess prebiotic properties that stimulate the growth of microorganisms. It was established that after 5–8 hours of cultivation, the number of viable cells of the studied cultures in the collagen substrate increases to 109 –1010 CFU / g. It is noted that the biomodification of rumina improves their organoleptic properties and consistency, causing it to become succulent, soft and ductile. Biotransformation of collagen-containing raw materials by probiotic microorganisms leads to a significant increase in amino acids in hydrolysates in comparison with the control sample. The greatest increase in amino acids is observed during the fermentation of collagen Lactobacillus helveticus H17-18, which indicates a higher proteolytic activity of this culture. It was shown that the rumen microstructure undergoes changes under the action of probiotic microorganisms in comparison with the initial state (the muscle carcass becomes thinner and looser, as well as undergoing change in terms of the structure of its morphological elements). As a result of the research, a fundamentally new scheme of biotechnological processing of collagen-containing raw materials was developed. The obtained results open up broad prospects for the creation of BAA-synbiotics and food products intended for functional nutrition.
A high demand for bacterial nanocellulose (BNC) in various economic sectors has resulted in intensification of studies aimed at searching for ways of reducing the cost of its production. BNC on an industrial scale is obtained using synthetic nutrient media, the cost of which may amount to 30–60% of the total cost of the process. Therefore, the study of BNC biosynthesis using low-cost nutrient media, such as food and cellulosic waste and other alternative sources of raw materials, seems to be highly relevant. The biomass of miscanthus currently used as a raw material for biofuels may become such an alternative source. Miscanthus is characterised by availability, low cost and annual renewability on an industrial scale. This study was aimed at investigating the BNC biosynthesis process from the enzymatic hydrolyzate obtained by alkaline delignification of miscanthus. The delignification process involved treatment of the plant with a dilute sodium hydroxide solution at ambient pressures. Enzymatic hydrolysis of the obtained substrate was carried out in a 11L-fermenter. For the first time, BNC was successfully obtained in a nutrient medium from an enzymatic hydrolyzate produced by alkaline delignification of miscanthus. The symbiotic culture of Medusomyces gisevii Sa-12 characterised by a high adaptive potential was used as a producer. The maximum specific growth rates were 0.360 and 0.384 day-1 for yeast and acetic acid bacteria, respectively. Consumption of reducing substances was observed to proceed in two stages: the rate constant of substrate utilisation at the first and the second stages were equal to 0.464 day and 0.034 day-1, respectively. The highest yield of BNC was 5.14% on the 14th day of cultivation, which is 1.8 times lower than that on a synthetic nutrient medium. Although the nutrient medium of the enzymatic hydrolyzate obtained by alkaline delignification of miscanthus is not biologically pure, Medusomyces gisevii Sa-12 shows a high technological potential and ability to synthesize a chemically pure BNC even under adverse conditions.
This article compares conventional (FeCl3, Al2(SO4)3) and innovative (Biokat P 500 и Nanofloc) reagents used in the combined biological and chemical wastewater treatment for coagulating medium components and microbial suspensions. In this study, we aimed to assess the effect of these reagents on the quantitative and species composition of microorganisms present in activated sludge. To that end, we modelled the processes of the combined biological and chemical wastewater treatment; cultivated samples of activated sludge and transferred them to selective media in order to establish the number of different physiological groups of microorganisms; as well as determined the taxonomic identity of bacterial colonies (nitrogen-fixing and phosphate-mobilizing bacteria). Changes in the biocoenosis of activated sludge were assessed for such agronomically important groups of microorganisms as diazotrophs, phosphate-mobilizing bacteria, actinobacteria, micromycetes, etc. It is established that combined biological and chemical wastewater treatment in most cases leads to a decrease in the number of these microorganisms. A notable decrease in the number of microorganisms in activated sludge samples containing a conventional reagent Al2(SO4)3 is experimentally confirmed. FeCl3 is shown to be the second most effective reagent in this respect. It is demonstrated that Nanofloc, despite inhibiting many studied groups of microorganisms, contributes to an increase in the number of diazotrophs; whereas the use of Biokat P 500 leads to the least negative consequences in terms of the number and composition of microorganisms present in activated sludge. In the course of identifying predominant nitrogen-fixing and phosphate-mobilizing bacteria via proteomic analysis, it is established that the following bacterial cultures are present in the control sample: Klebsiella oxytoca, Pseudomonas putida, Acinetobacter johnsonii, Rhodococcus erythropolis. These microorganisms are known for playing a significant role in ecology and biotechnology. Following addition of FeCl3 to the test samples, only one bacterial culture (K. oxytoca) was found to be predominant; whereas addition of innovative reagents resulted in two predominant bacterial cultures (Biokat P 500 – Enterobacter ludwigii and Aeromonas veronii; Nanofloc – Enterobacter cloacae and R. erythropolis). The presence of several dominant bacterial species, belonging to other groups than nitrogen-fixing or phosphate-mobilizing bacteria, may indicate the syntrophic nature of activated sludge communities.
CHEMICAL TECHNOLOGY
This article describes the formation of an effective sorbent for heavy metal ions by modifying natural zeolite (clinoptilolite type, Kholinskoye deposit). The modification was carried out by applying the network of a sulphur-containing polymer on the zeolite surface. For the formation of a polymer network, elemental sulphur was dissolved in the hydrasine hydrate–monoethanolamine system to generate polysulphide anions (in particular, S22-). During the contact of the obtained sulphur solution with zeolite, polysulphide anions and the monoethanolamine entering the zeolite pores were concentrated on the surface. Further polycondensation of S22- anions with 1,2,3-trichloropropane (epichlorohydrine production waste) resulted in the formation of a reticulated sulphur-containing polymer covering the zeolite surface. Such a sorbent provides immediate solution to the problems concerned with utilisation of organochlorine wastes and purification of technological media containing heavy metals. Extraction of metals by the obtained sorbent was studied using model solutions with a metal concentration of 5000 mg/L. Encouraging results were obtained for five metals. Detailed information on the extraction of copper ions from aqueous solutions is presented. Experimental data was obtained on the effect of pH on the sorption efficiency of copper ions, as well as on the thermodynamic and kinetic characteristics of adsorption under static and dynamic conditions. The complex coordination mechanism of Cu (II) sorption by modified zeolite was confirmed using IR-spectroscopy. Since the thermodynamic and kinetic dependencies frequently deviate from the classical laws during sorption by the complex coordination mechanism, regression analysis was used to process the experimental data. As the result, nonlinear models were obtained fairly accurately describing experimental data on the extraction of copper ions by modified zeolite. The obtained regression models can be applied in further research of the new sorbent and in designing installations for extracting copper compounds from technological media.
ISSN 2500-1558 (Online)