Volume 67, Nº 6 (2018)

The review addresses the special case of mechanical activation of solid-state chemical reactions when the stress field, strain, and defects in crystals are induced by the chemical reaction itself rather than by the external mechanical impact (chemo-mechanochemical (CMC) effect). This review presents the analysis and state-of-the-art of research activities in this area. Different cases of the CMC effect in homogeneous and heterogeneous systems are considered: with or without changes in the chemical composition, with or without formation of solid products, etc.

The role of natural radioactivity in the formation of the oxygen atmosphere of the Earth is discussed. The origination of oxygen in the free state in the hydrosphere and atmosphere is associated with the radiolysis of the water of the World ocean under the irradiation of radio active isotopes ⁴⁰K, ²³⁵U, ²³⁸U, and ²³²Th. The calculations showed that within the last 3.8 billion years the total weight of oxygen, which could be formed due to this process, is about 7.4•10¹⁷ kg, i.е., the value of the same order as the oxygen content in the modern atmosphere of the Earth. The Ocean was an intermediate collector and provided the nucleation of new forms of biological life with oxygen respiration. The consecutive transformation of the Earth’s atmosphere with a gradual increase in the oxygen content became the result of photosynthesis in algae and green plants and thus opened a way to the origination of complicated forms of the life.

The computational simulation of structure, energy and spectral characteristics of spiropyrans and their complexes with the cluster containing ten silver atoms was carried out using the density functional theory method (B3LYP/6-31G(d,p)/SDD). A competitive coordination of oxygen-containing substituents in the indoline and benzopyran moieties in spirocyclic molecules to the metal atoms was studied and an effect of position of donor groups on the activity of CO vibrational bands was established in the calculated Raman spectra. We revealed compounds, whose trans-trans-trans isomers upon a complexation with the silver cluster are characterized by the more than 100 times enhanced activity of band associated with the valence vibrations of CO bond in the Raman spectrum.

Graphene oxide was obtained from expanded graphite according to the modified Hummers method. The reaction time was significantly reduced (from 24 to 8 h) by applying the expanded graphite in the oxidation process. The interlayer distance in obtained samples was equal to 0.70–0.74 nm. Structural features of the material were studied by the powder X-ray diffraction, thermogravimetric analysis, scanning electron microscopy, transmission electron microscopy, XPS spectroscopy, and NMR spectroscopy.

Active carbons were synthesized from a furfural copolymer using a polyester resin as an activator. The influence of the temperature of the thermal treatment of the carbon sorbents on the weights and ash contents of the obtained materials was established. The molecular structures of the carbons were studied by NMR spectroscopy.

Methods of synthesizing silver nanoparticles (SNP) of various sizes stabilized with a maleic acid copolymer are proposed. The colloidal solutions of SNP are characterized by electron spectroscopy, static and dynamic light scattering, transmission electron microscopy. The stability of the obtained SNP in solutions of hydrogen peroxide and a hydrochloric acid salt is studied, their efficiency in antimicrobial activity tests is assessed.

The catalytic activity of the colloidal catalyst based on iron(III) hydroxide was studied in the decomposition of H₂O₂ in a neutral medium (pH 6.7). A colloidal micellar solution of iron(III) hydroxide after preparation was kept at 19–20 °С for 2 or 20 h without additives or with C₂H₅OH additives. The decomposition of H₂O₂ under the action of the colloidal catalyst (20 h) proceeds via the first-order reaction with the decay rate constant k_d = 1.26•10^–4 s^–1, whereas the decay rate of the first-order reaction is k_d = 0.77•10^–4 s^–1 for the colloidal catalyst (2 h) prepared in the presence of C₂H₅OH.

Synthesis of catalysts based on hyperbranched pyridylphenylene polymer and palladium nanoparticles (РРР-Рd) is described. Catalytic activity in the Suzuki—Miyaura cross-coupling reaction is studied for the interaction of bromobenzene with phenylboronic acid. Optimal reaction conditions providing maximum conversion (100%) of the initial compounds are established.

The evolution of dielectric properties during the cyanate ester oligomer curing process was studied in the electric field frequencies range of 10^–2—10⁵ Hz. The kinetic of the curing process was investigated using the acquired data for complex dielectric permittivity and conductivity. It is demonstrated that, along with the formation of the polymer network, a microphase separation of the reaction intermediate, namely carbamate, takes place during the trimerization reaction. It is manifested in the frequency spectra as the Maxwell—Wagner polarization.

A series of 1,3-disubstituted 4-benzylideneamino-5-thioxohexahydroimidazo[4,5-d]imidazol-2(1H)-ones (thioglycolurils) was synthesized via the reaction of 5,7-disubstituted 3-thioxoperhydroimidazo[4,5-e]-1,2,4-triazin-6-ones with hydroxy-, alkoxy-, and fluorocontaining benzaldehyde derivatives. An alkylation of the obtained thioglycolurils with methyl iodide or 4-bromobenzyl bromide provided the corresponding 6-benzylideneamino-5-alkylsulfanyl-3,3a,6,6a-tetrahydroimidazo[4,5-d]imidazol-2(1H)-ones. The fungicidal activity of some synthesized compounds against pathogens causing diseases of agricultural crops was studied.

An effective synthesis of polynuclear tetraamines via nucleophilic substitution of chlorine in 2-chloro-5-nitroaniline under ultrasonic irradiation followed by catalytic hydrogenation of dinitrodiaminoarenes in a flow reactor was proposed. A number of monomers, including those not described in the literature, were thus obtained. Two classes of polyheteroarylenes, namely, polynaphthoylenebenzimidazoles and polyphenylquinoxalines were synthesized by the polycyclocondensation in a supercritical carbon dioxide. Incorporation of trifluoromethyl substituents and flexible oxygen bridges into the structure of monomers allowed one to improve the solubility of the polymers. Some properties of synthesized polyheteroarylenes were investigated.

Chlorination of 1-hydroxyindole-5,6-dicarbonitriles and 1-hydroxypyrrolo[3,4-f]indole-5,7(1H,6H)-diones with N-chlorosuccinimide afforded previously unknown 3,3-dichloro-3Hindole 1-oxides instead of the expected 3-chloro-1-hydroxyindoles. The latter, however, were prepared in good yields by treatment of the above 3,3-dichloro-3H-indole 1-oxides with piperidine in ethanol. Reduction of 3,3-dichloro-5,6-dicyano-3H-indole 1-oxides with Zn in AcOH yielded the corresponding 3-chloroindole-5,6-dicarbonitriles.

A new approach to radical accelerate large-scale quantum chemical calculations of docking complexes, which require large computational times, is proposed. It takes into account the local nature of protein interaction with ligands and is based on a formation of special groups of atoms, which include the compactly located ligands and the protein atoms surrounding them. The procedure based on this approach allowed more than twice to reduce the time of a very resource-consuming calculation with respect to our previous high-speed semi-empirical method without a noticeable decrease in accuracy and provided a level of the time consumption appropriate for the large-scale serial calculations of such complexes.

The reactions of thiosemicarbazide (TSC), thiocarbohydrazide, and hydrazine thiocarbamate with oxyketones, haloketones, and derivatives of acetylenic alcohols were studied. Thiadiazines bearing exocyclic thio and hydrazo groups were synthesized. Acetylenic alcohols react with TSC to give the corresponding thiazolidines. The reactions of halo derivatives of acetylenic alcohols with TSC are complicated by side reactions.