Vol 512, No 1 (2023)

The analysis of the literature data on the set of reactions for the production of macromolecules with a high content of phosphorus and sulfur is carried out, and the main approaches allowing to involve these elements in the composition of polymers and polymer materials, considering the fundamental principles of green chemistry, are considered. The methods leading to the formation of functional polymers under mild conditions with minimal energy consumption from external sources necessary for the synthesis, which can become new growth points of green industrial technologies, are considered. Particular attention is paid to the issues of synthesis of polyphosphazenes and polyphosphoesters for biomedical purposes, as well as the inverse vulcanization reaction with the formation of polymers that are used in sorption wastewater treatment, the creation of current sources and IR optics.

Based on monoterpenoid (–)-isopulegol a number of new derivatives of octahydro-2H-chromene have been synthesized. The structure of the products obtained was determined by ¹H and ¹³C NMR spectroscopy, high resolution mass spectrometry and X-ray diffraction analysis. It was shown that several synthesized compounds exhibit high analgesic activity in in vivo tests. The highest efficiency in both tests (acetic writhing and hot plate) was shown by (4S)-diastereomers of morpholinoacetamide derivatives of octahydro-2H-chromene.

The activating effect of AlCl₃ in the amount of 10 mol. % in the homo-coupling of alkyl-, phenyl-, and silyl-substituted acetylenes with the Mg–Cp₂ZrCl₂ reagent system was found for the first time. The unique nature of this activation is indicated by the fact that in the presence of 10 mol. % of Lewis acids such as BF₃ ⋅ Et₂O, Me₃SiCl, InCl₃, and SnCl₄, the reaction with 5-decyne does not occur even after 5 h, while in the presence of AlCl₃, homocoupling products are selectively formed in high yield in 10 min at room temperature.

New dialkyldithio derivatives of 2,6-dimethylphenol have been synthesized and characterized. For the first time, the polyfunctional properties of these compounds have been studied as additives to lubricating oils in the processes of friction and wear in the boundary friction regime, as inhibitors of high-temperature oxidation of hydrocarbons, and as protectors of metal surfaces. It has been established that already with the content of synthesized additives in lubricating oils in the amount of 0.5 wt. % antiwear properties are improved more than twice. It has been shown that additives exhibit a complex antioxidant effect and high efficiency at all stages of the oxidation process, and even at ultra-low concentrations (0.005 wt. %), their ability to resist oxidation exceeds widely used analogs. New additives are of considerable interest to modern lubrication science, and they can be used in motor oil compositions and other lubricants.

A new method for the synthesis of 5,5-disubstituted N-methyl-1,3-oxazinanes as a mixture of diastereomers at position 5 containing monoterpene and branched alkyl substituents at position 5 has been developed. The 1,3-oxazinanes were obtained for the first time by the interaction of 2,2-substituted 3-aminopropane-1-ols with formaldehyde and sodium borohydrides in a single stage.

In this work, we consider the effect of carbon supports and methods of preparing Pd/C catalysts on the ability of palladium-containing particles to leach out into solution during the interaction of a catalyst with a solvent. The leaching of palladium particles from the substrate surface into pure solvents was studied by high resolution mass spectrometry. It is shown that the type of leached palladium particles formed in the solution depend not only on the solvent, but also on the method of catalyst preparation and on the nature of the support. It has been found that the use of phosphorus-doped carbon (PC) as a support also results in palladium being leached into solution. In addition, the catalytic activity of the catalysts supported on graphite and PC equally decreased both in the Suzuki–Miyaura reaction and in the Mizoroki–Heck reaction.

For the first time, an approach to designing the structure of Eu²⁺ containing silicate glass-ceramics materials has been experimentally implemented, which consists in the fact that rare earth activator is introduced into various crystals formed during glass crystallization. Transparent Eu-containing glass and glass ceramics based on the system BaO–ZrO₂–SiO₂–MgF₂ were prepared by the traditional glass melting method at 1450°C. The crystal structure and properties of materials were characterized by XRD analysis and photoluminescence spectroscopy during different stages of glass crystallization. It is shown that the simultaneous incorporation of Eu into different silicate crystals (Ba₂SiO₄, BaMgSiO₄, and BaSiO₃) formed during the glass crystallization leads to the formation of a material with a wide luminescence band in the visible part of the spectrum. The study of photoluminescence and luminescence excitation spectra of the glass suggests the possibility of energy transfer from Eu²⁺ to Eu³⁺ ions. The structures of Eu²⁺ luminescent centers are similar in the glass and glass-ceramics that is related to some phase separation in the glass before crystallization. The study of luminescence properties of prepared materials showed that these materials can be promising for the application in LEDs techniques.

Large molecules of dyes or other substances can play the role of a nano-adsorbent in aqueous surfactant solutions and, coated with surfactant molecules, resemble surfactant micelles with a solubilizate. Such micelle-like particles were called protomicelles. Their formation does not require a critical micelle concentration (CMC) and begins immediately when the surfactant is introduced into the solution. In this spectrophotometric study of Nile red (NR) in aqueous solutions of nonanoic acid (NOA), the case where protomicelles are more important than micelles is demonstrated for the first time. It has been shown that the solubilization of NR in both premicellar and micellar solutions proceeds through protomicelles rather than NOA micelles. The article also contains a theoretical part. In it, on the basis of the chemical potential of the nano-adsorbent, it is proved that the addition of a surfactant to a solution always increases the solubility of the nano-adsorbent. The dependence of adsorption on the curvature of the nano-adsorbent surface is considered and it is shown that the adsorption equations for flat surfaces can be used for curved surfaces with high accuracy.

Dissipative particle dynamics were used for the first time to simulate the reaction of biphasic catalysis with microgels adsorbed at the phase boundary with catalytic groups. It is shown that the rate of the catalytic process increases with the degree of deformation of the polymer network, which depends on the amount of the crosslinker and the solubility of the polymer in both phases. In this case, the highest rate of catalysis was observed for the microgel soluble in both phases due to an increase in its porosity (compared to amphiphilic microgels) and the “water–microgel–oil” contact area with a simultaneous decrease in the time for reagents to reach the catalytic groups due to the flattening of the microgel. The results obtained can be useful for increasing the efficiency of a wide range of catalytic reactions of the considered type through the use of network macromolecules.