


Vol 487, No 1 (2019)
- Year: 2019
- Articles: 11
- URL: https://journals.rcsi.science/0012-5008/issue/view/9320
Chemistry



Dinuclear Cobalt and Iron Complexes with an Azomethine Derivative of 1,10-Phenanthroline: A Quantum-Chemical Study
Abstract
Geometries, energies, and magnetic characteristics of dinuclear cobalt and iron complexes with 5,6-bis(salicylideneimino)-1,10-phenanthroline have been studied by the density functional theory method (DFT UTPSSh/6-311++G(d,p)). Complexes containing two magnetically active moieties capable of exhibiting spin crossover and valence tautomerism have been constructed by completing the metal coordination sphere with ancillary ligands. These effects provide for the variation of spin states in a wide range, which gives the studied compounds properties of molecular switches and spin qubits.



Peptide Derivatives of Some Physiologically Active Substances
Abstract
The synthesis of Boc-Gly-Pro-Dox, Boc-Gly-Pro-DOPA, and Boc-Gly-Pro-Srt and their deuterated analogues was carried out. The condensation is accompanied by side reactions, which could be minimized by optimizing the reaction conditions. The most versatile approach to the synthesis of Boc-Gly-Pro-Dox, Boc-Gly-Pro-DOPA, and Boc-Gly-Pro-Srt and their deuterated analogues is condensation of Boc-Gly-Pro or Boc-Gly-[2H]Pro with the amino groups of dopamine, serotonin, and doxorubicin. For the introduction of hydrogen isotopes into ΔPro, hydrogenation of its aqueous solution followed by condensation of the reduced proline with Boc-GlyOSu is recommended. Mass spectrometry was used to determine the content of isotopomers in the deuterated products.



Reduction of Acridine and 9-Chloroacridine with Red Phosphorus in the KOH/DMSO System
Abstract
Acridine reacts with red phosphorus in the KOH/DMSO(H2O) system on heating (100°C, 3 h) to give 9,10-dihydroacridine regioselectively in quantitative yield. Under similar conditions, 9-chloroacridine reacts with Pred/KOH/DMSO(H2O) system to afford 9,10-dihydroacridine and acridone in 51 and 40% yield, respectively.



A New Method for Synthesis of Binary Borides with Desired Properties
Abstract
Complexes [Co(solv)n][B10H10], where (I: solv = H2O, n = 6; II: solv = N2H4, n = 3) have been synthesized and characterized. The possibility to use them as precursors in the synthesis of binary borides has been demonstrated. The purity and homogeneity of the precursors and the products of their thermal reduction (in an inert atmosphere at 650 and 900°С) has been established by elemental analysis, X-ray powder diffraction, and IR spectroscopy; magnetochemical studies of the precursors and their annealing products have been carried out. According to the data obtained, the reduction products are structured oxide-boride and nitride-boride phases, respectively. Magnetochemical study of the phases has revealed a significant difference in their magnetic behavior: the oxide-boride phase is characterized by a significant ferromagnetic contribution to the total magnetization of the sample, while the nitride-boride phase, by a diamagnetic contribution.



Formation of Nanowhiskers in Tungsten-Containing Syntactic Foam under Nanosecond Relativistic Electron Beam
Abstract
The formation of nanowhiskers in tungsten-containing syntactic foam under nanosecond relativistic electron beam has been experimentally studied. It has been demonstrated that a single impact of relativistic electron beam with a flux density of 230–240 J/cm2 and a total pulse duration of 150 ns on syntactic foam leads to the collapse of microspheres of more than 40 μm in diameter with the formation of filamentous structures up to 10 μm in length and about 100 nm in diameter on their surface. There is complex kinetics of substance ablation from the irradiated surface at a gas-plasma formation expansion rate of ~13 km/s. It has been found that nanowhiskers do not form near the emission “crater” from syntactic foam where the duration of the mechanical pressure pulse is minimal and close to the relativistic electron beam impact.






Catalytic Isomerization of Substituted Vinylcyclopropanes
Abstract
The catalytic isomerization of substituted vinyl-gem-dichlorocyclopropanes in the presence of a series of zeolite catalysts has been studied. It has been shown that substituted gem-dichlorocyclopentenes are the sole reaction products. The influence of a number of factors (the type of catalyst, temperature, and reaction time) on the yield of isomerization products has been investigated.



Chemical Technology
A New Approach to Performing Thermally Coupled Processes by the Example of a (Ni + Al)–(Ti + C) Granular Mixture
Abstract
For the first time, for performing thermally coupled SHS processes, granular mixtures were used instead of powder ones. In this case, the rate of the heat transfer between the donor and the acceptor is virtually independent of the sample size and is determined only by the granule size. Therefore, an advantage of using a granular mixture is that the process optimized under laboratory conditions can be scaled without changing its characteristics and the properties of the desired synthesis product. The studied granular mixture comprised a mixture of (Ni + Al) granules (acceptor) and a mixture of (Ti + C) granules (donor), which differed in rate and temperature of combustion. It was determined that the ignition of the (Ni + Al) acceptor granules occurred in the combustion front. It was shown that using granular mixtures for performing coupled thermal reactions makes it possible to obtain the combustion products as a readily destructible sample, from which the desired product can be separated even if the melting point of the product of the interaction of the acceptor mixture is lower than the adiabatic combustion temperature.



Production of Methane Hydrates in Dispersed Frozen Aqueous Solutions of Polyvinyl Alcohol
Abstract
The paper presents the first results of studying the kinetics of the formation of methane hydrates in dispersed frozen aqueous solutions of polyvinyl alcohol (FAS PVA) near the ice melting point under static conditions (without stirring). Based on the obtained experimental data, it was determined for the first time that using FAS PVA significantly (severalfold) decreases the time of conversion of much of the initial water into hydrate in comparison with dispersed ice. Furthermore, it was shown that the formation of gas hydrates in FAS PVA dispersions under static hydrate formation conditions can occur not only at higher rate but also at higher water-to-hydrate conversion in comparison with those in aqueous solutions of surfactants or in “dry water.”



Mineral–Polymer Composites Based on Hydroxyapatite and Polyvinylpyrrolidone for Medical Applications
Abstract
Hydroxyapatite (HA)–polyvinylpyrrolidone (PVP) nanocomposites with the HA/PVP ratio of 3.6–14.5 were synthesized by chemical precipitation from solutions of calcium nitrate and ammonium hydrogen phosphate in a PVP solution. The phase composition, size of coherent scattering regions, and size and morphology of HA particles were determined after heat treatment of the products of synthesis. The chemical interaction of the composite components was established by ESR spectroscopy on exposure to laser radiation at 355 nm.


