D. Mendeleyev University of Chemical Technology of Russia

In the current context of the pandemic triggered by SARS-COV-2, the immunization of the population through vaccination is recognized as a public health priority. In the case of SARS‑COV‑2, the genetic sequencing was done quickly, in one month. Since then, worldwide research has focused on obtaining a vaccine. This has a major economic impact because new technological platforms and advanced genetic engineering procedures are required to obtain a COVID‑19 vaccine. The most difficult scientific challenge for this future vaccine obtained in the laboratory is the proof of clinical safety and efficacy. The biggest challenge of manufacturing is the construction and validation of production platforms capable of making the vaccine on a large scale.

The hydrogen bond (H-bond) energies are evaluated for 18 molecular crystals with 28 moderate and strong O-H···O bonds using the approaches based on the electron density properties, which are derived from the B3LYP/6-311G** calculations with periodic boundary conditions. The approaches considered explore linear relationships between the local electronic kinetic G(b) and potential V(b) densities at the H···O bond critical point and the H-bond energy E(HB). Comparison of the computed E(HB) values with the experimental data and enthalpies evaluated using the empirical correlation of spectral and thermodynamic parameters (Iogansen, Spectrochim. Acta Part A 1999, 55, 1585) enables to estimate the accuracy and applicability limits of the approaches used. The V(b)-E(HB) approach overestimates the energy of moderate H-bonds (E(HB) < 60 kJ/mol) by ~20% and gives unreliably high energies for crystals with strong H-bonds. On the other hand, the G(b)-E(HB) approach affords reliable results for the crystals under consideration. The linear relationship between G(b) and E(HB) is basis set superposition error (BSSE) free and allows to estimate the H-bond energy without computing it by means of the supramolecular approach. Therefore, for the evaluation of H-bond energies in molecular crystals, the G(b) value can be recommended to be obtained from both density functional theory (DFT) computations with periodic boundary conditions and precise X-ray diffraction experiments.

The computer program WinXPRO enables the calculation of crystal and molecular properties using the multipole parameters of the electron density. The list of properties includes the electron density and its topological and electric field characteristics, the local kinetic and potential energies, the electron localization function, and the effective crystal potential. WinXPRO works under the Windows operating system and can utilize any existing graphics program to display output.

The properties of nanoemulsions and various methods for their preparation including the high-energy and low-energy emulsification methods and the combined methods are reviewed. Among the high-energy methods, the emphasis is placed on high-energy stirring, ultrasonic emulsification, high-pressure homogenization including microfluidics and membrane emulsification. Among the low-energy emulsification methods, the attention is focused on the phase inversion temperature method, the emulsion inversion point method and the spontaneous emulsification. Using a combined method, which includes the high-energy and low-energy emulsification, it is possible to prepare reverse nanoemulsions in highly viscous systems. Main advantages and limitations of different methods of nanoemulsion preparation are discussed and the potential fields of nanoemulsion applications are considered. The bibliography includes 255 references.

Extracellular matrix (ECM) is an extraordinarily complex and unique meshwork composed of structural proteins and glycosaminoglycans. The ECM provides essential physical scaffolding for the cellular constituents, as well as contributes to crucial biochemical signaling. Importantly, ECM is an indispensable part of all biological barriers and substantially modulates the interchange of the nanotechnology products through these barriers. The interactions of the ECM with nanoparticles (NPs) depend on the morphological characteristics of intercellular matrix and on the physical characteristics of the NPs and may be either deleterious or beneficial. Importantly, an altered expression of ECM molecules ultimately affects all biological processes including inflammation. This review critically discusses the specific behavior of NPs that are within the ECM domain, and passing through the biological barriers. Furthermore, regenerative and toxicological aspects of nanomaterials are debated in terms of the immune cells-NPs interactions.

Studies on the structure and properties of complexes and crystals with halogen bonding accompanied by different secondary non-covalent interactions are summarized. The signs of halogen bonding are systematized and modern methods and approaches used to provide clear and reproducible estimates of the strength of halogen bonds are analyzed. The halogen bond strength values are compared with the strength of the other non-covalent interactions. The contradictions in the interpretation of the results from different studies of the strength of halogen bond are discussed. The bibliography includes 249 references.

This paper discusses the mechanism of montmorillonite structural alteration and modification of bentonites’ properties (based on samples from clay deposits Taganskoye, Kazakhstan and Mukhortala, Buriatia) under thermochemical treatment (treatment with inorganic acid solutions at different temperatures, concentrations and reaction times). Treatment conditions were chosen according to those accepted in chemical industry for obtaining acid modified clays as catalysts or sorbents. Also, more intense treatment was carried out to simulate possible influence at the liquid radioactive site repositories. A series of methods was used: XRD, FTIR, ICP-AES, TEM, nitrogen adsorption, and particle size analysis. It allowed revealing certain processes: transformation of montmorillonite structure which appears in the leaching of interlayer and octahedral cations and protonation of the interlayer and –OH groups at octahedral sheets. In turn, changes in the structure of the 2:1 layer of montmorillonite and its interlayer result in significant alterations in the properties: reduction of cation exchange capacity and an increase of specific surface area. Acid treatment also leads to a redistribution of particle sizes and changes the pore system. The results of the work showed that bentonite clays retain a significant portion of their adsorption properties even after a prolonged and intense thermochemical treatment (1 M HNO3, 60 °C, 108 h).

Copper-containing coordination compounds attract wide attention due to the redox activity and biogenicity of copper ions, providing multiple pathways of biological activity. The pharmacological properties of metal complexes can be fine-tuned by varying the nature of the ligand and donor atoms. Copper-containing coordination compounds are effective antitumor agents, constituting a less expensive and safer alternative to classical platinum-containing chemotherapy, and are also effective as antimicrobial, antituberculosis, antimalarial, antifugal, and anti-inflammatory drugs. 64Cu-labeled coordination compounds are promising PET imaging agents for diagnosing malignant pathologies, including head and neck cancer, as well as the hallmark of Alzheimer’s disease amyloid-β (Aβ). In this review article, we summarize different strategies for possible use of coordination compounds in the treatment and diagnosis of various diseases, and also various studies of the mechanisms of antitumor and antimicrobial action.

The chemistry of heterocyclic compounds has traditionally been and remains a bright area of chemical science in Russia. This is due to the fact that many heterocycles find the widest application. These compounds are the key structural fragments of most drugs, plant protection agents. Many natural compounds are also derivatives of heterocycles. At present, more than half of the hundreds of millions of known chemical compounds are heterocycles. This collective review is devoted to the achievements of Russian chemists in this field over the last 15–20 years. The review presents the achievements of leading heterocyclists representing both RAS institutes and university science. It is worth noting the wide scope of the review, both in terms of the geography of author teams, covering the whole of our large country, and in terms of the diversity of research areas. Practically all major types of heterocycles are represented in the review. The special attention is focused on the practical applications of heterocycles in the design of new drugs and biologically active compounds, high-energy molecules, materials for organic electronics and photovoltaics, new ligands for coordination chemistry, and many other rapidly developing areas. These practical advances would not be possible without the development of new fundamental transformations in heterocyclic chemistry.&lt;br&gt; Bibliography — 2237 references.

A series of novel non-symmetrical coumarin-fused BODIPY dyes were synthesised. Their absorption and emission properties are strongly influenced by substitution in the coumarin moiety. Diethylamino-substituted dyes showed near-IR emission with large Stokes shifts (up to 144 nm) and good fluorescence quantum yields.

Hydrogen bonding in ionic liquids based on the 1-(2'-hydroxylethyl)-3-methylimidazolium cation ([C₂OHmim](+)) and various anions ([A](-)) of differing H-bond acceptor strength, viz. hexafluorophosphate [PF6](-), tetrafluoroborate [BF₄](-), bis(trifluoromethanesulfonimide) [Tf₂N](-), trifluoromethylsulfonate [OTf](-), and trifluoroacetate [TFA](-), was studied by a range of spectroscopic and computational techniques and, in the case of [C₂OHmim][PF6], by single crystal X-ray diffraction. The first quantitative estimates of the energy (E(HB)) and the enthalpy (-ΔH(HB)) of H-bonds in bulk ILs were obtained from a theoretical analysis of the solid-state electron-density map of crystalline [C₂OHmim][PF6] and an analysis of the IR spectra in crystal and liquid samples. E(HB) for OH···[PF6](-) H-bonds amounts to ~3.4-3.8 kcal·mol(-1), whereas weaker H-bonds (2.8-3.1 kcal·mol(-1)) are formed between aromatic C2H group of imidazolium ring and the [PF6](-) anion. The enthalpy of the OH···[A](-) H-bonds follows the order: [PF6] (2.4 kcal·mol(-1)) < [BF₄] (3.3 kcal·mol(-1)) < [Tf₂N] (3.4 kcal·mol(-1)) < [OTf] (4.7 kcal·mol(-1)l) < [TFA] (6.2 kcal·mol(-1)). The formation of aggregates of self-associated [C₂OHmim](+) cations is present in liquid [C₂OHmim][PF6], [C₂OHmim][BF₄], and [C₂OHmim][Tf₂N], with the energy of the OH···OH H-bonds amounting to ~6 kcal·mol(-1). Multiple secondary interactions in the bulk ILs influence their structure, vibrational spectra, and H-bond strength. In particular, these interactions can blue-shift the stretching frequencies of the CH groups of the imidazolium ring in spite of red-shifting CH···[A](-) H-bonds. They also weaken the H-bonding in the IL relative to the isolated ion pairs, with these anticooperative effects amounting to ca. 50% of the E(HB) value.

Carbon nanotubes (CNTs) and carbon nanofibers (CNFs) are known to possess exceptional tensile strength, elastic modulus and electrical and thermal conductivity. They are promising candidates for the next-generation high-performance structural and multi-functional composite materials. However, one of the largest obstacles to creating strong, electrically or thermally conductive CNT/CNF composites is the difficulty of getting a good dispersion of the carbon nanomaterials in a matrix. Typically, time-consuming steps of purification and functionalization of the carbon nanomaterial are required. We propose a new approach to grow CNTs/CNFs directly on the surface of matrix particles. As the matrix we selected cement, the most important construction material. We synthesized in a simple one-step process a novel cement hybrid material (CHM), wherein CNTs and CNFs are attached to the cement particles. The CHM has been proven to increase 2 times the compressive strength and 40 times the electrical conductivity of the hardened paste, i.e. concrete without sand.

This paper presents an analysis of the observed combustion behavior of AN mixtures with different additives, fuels, and energetic materials. It has been determined on the basis of flame structure investigation by fine tungsten-rhenium thermocouples that the surface temperature of AN is controlled by the dissociation reaction of the salt occurring at the surface. Results obtained have indicated that the leading reaction of combustion of AN doped with additives proceeds in the condensed phase up to pressures of 20–30 MPa. A reason for the inability of pure AN to burn is suggested and the role of additives in the combustion mechanism is discussed.

Neuropsychiatric diseases are one of the main causes of disability, affecting millions of people. Various drugs are used for its treatment, although no effective therapy has been found yet. The blood brain barrier (BBB) significantly complicates drugs delivery to the target cells in the brain tissues. One of the problem-solving methods is the usage of nanocontainer systems. In this review we summarized the data about nanoparticles drug delivery systems and their application for the treatment of neuropsychiatric disorders. Firstly, we described and characterized types of nanocarriers: inorganic nanoparticles, polymeric and lipid nanocarriers, their advantages and disadvantages. We discussed ways to interact with nerve tissue and methods of BBB penetration. We provided a summary of nanotechnology-based pharmacotherapy of schizophrenia, bipolar disorder, depression, anxiety disorder and Alzheimer's disease, where development of nanocontainer drugs derives the most active. We described various experimental drugs for the treatment of Alzheimer's disease that include vector nanocontainers targeted on β-amyloid or tau-protein. Integrally, nanoparticles can substantially improve the drug delivery as its implication can increase BBB permeability, the pharmacodynamics and bioavailability of applied drugs. Thus, nanotechnology is anticipated to overcome the limitations of existing pharmacotherapy of psychiatric disorders and to effectively combine various treatment modalities in that direction.

The ionic liquids 1-allyl-3-methylimidazoliumchloride[Amim][Cl] and 1-butyl-3-methylimidazoliumchloride[Bmim][Cl] were utilized in the dissolution of different natural cellulose biopolymers. The biopolymers subject to this investigation were microcrystalline cellulose, cotton linters as well as Kraft cellulose cut to 0.35 mm fibres. High-intensity acoustic irradiation by means of an ultrasonic horn was applied to enhance the dissolution process. The ionic liquids investigated were able to dissolve cellulose at elevated temperatures, in high concentrations, although significant differences were observed, depending on the type of cellulose and ionic liquid. Moreover, the dissolution process under conventional heating was rather slow, typically extending for a period of several hours. Upon use of high-power ultrasound, the dissolution process was dramatically intensified and complete dissolution was achieved in a matter of few minutes only. Various approaches to cellulose functionalization were proposed and investigated. The effect of external parameters, such as the reaction temperature, the cellulose–derivatising agent molar ratio and the batch time of experiment were studied. Various physico-chemical methods, such as acid methanolysis, TGA, DSC, SEM as well as NMR on 1H and 13C nuclei were applied to investigate the structure and morphology of both the cellulose samples and ionic liquids before and after processing.

The review concerns the main chemical and physicochemical properties and the methods of modification of carbon nanotubes, a novel promising material. The feasible and potential fields of applications of carbon nanotubes are outlined. The bibliography includes 573 references.

Chemical bonding in the pentaerythritol tetranitrate crystal based on the experimental electron density obtained from X-ray diffraction data at 100 K and theoretical calculations at the experimental molecular geometry have been analyzed in terms of the Quantum Theory of Atoms in Molecules. Features of the intra- and intermolecular bond critical points and the oxygen atom lone-pair locations are discussed. Numerous intermolecular bonding interactions, including O...H and O...O, have been found and characterized. Atomic charges and atomic energies were integrated and compared with those for similar compounds. The N-O topological bond orders have been calculated for the first time, and the PETN atomic valences have been estimated.

The use of polymers is restricted by their flammability - they may indeed initiate or propagate fire. Fire Retardancy of Polymers focuses on mineral additives from either micro- or nano-composites for application in fire retardants. With the use of fire retardant additives containing halogen or phosphorus compounds in decline, the need for other systems is evident. The major materials that are used are alumina trihydrate or magnesium hydroxide which account for more than 50% by weight of the world-wide sales of fire retardants. Recent works have shown that such halogen-free compounds may give enhanced fire retardancy to polymeric materials when used in low levels, alone, or in synergistic mixtures. The corresponding fire performance depends on the dispersion of the mineral filler, with micrometer-scale dispersion leading to the best performances. Specialists discuss these new applications of mineral fillers with particular emphasis on action mechanisms, new materials including textiles, toxicology and hazards. With extensive references, this book provides a comprehensive and up-to-date view of these applications. This book will appeal to professionals, materials scientists and engineers looking for novel ways to eliminate fire hazards and improve flame retardancy of materials, with a special interest in sustainable development.

This article aims to develop a method for regenerating and reusing carbon and glass fibers extracted from unrecyclable scraps of carbon plastics, printer parts, and laminating coating. A comparison of known methods of fiber regeneration revealed the advantages of thermal treatment: absence of costs of reagents and complex equipment; better preservation of composition; and strength of fibers. Based on the results of thermographic analysis of wastes in nitrogen and air, the destruction temperatures of their organic matrices were determined (200-460°С), and the use of calcination instead of pyrolysis was justified. The appearance and surface quality of the regenerated fibers are characterized by optical and electron microscopy. It has been established that quantitative extraction of pure carbon and glass fibers from waste crushed to 1 cm is efficient by their calcination at 700 °C for 0.5 h and 500 °C for 1 h, respectively. The principle of creating new composites with the obtained fibers based on the similarity of their composition and binding materials (matrices) has been proposed. It was shown that the introduction of 1 wt% of fibers into slag blocks and active carbon pellets considerably increases their compressive strength, but the bending strength does not change due to dispersed reinforcement. Possible improvement of mechanical properties of products requires reagent treatment of the fiber surface or the introduction of binder additives. Calculations show that the developed method of recycling composite waste can produce 2.3 tons/hour of reinforced building materials that are good for the environment and the economy, excluding expenses for landfill waste disposal and reducing the cost of the product by replacing the primary fiber for the secondary one. Doi: 10.28991/ESJ-2022-06-05-04 Full Text: PDF

Toxicological research of novel nanomaterials is a major developmental step of their clinical approval. Since iron oxide magnetic nanoparticles have a great potential in cancer treatment and diagnostics, the investigation of their toxic properties is very topical. In this paper we synthesized bovine serum albumin-coated iron oxide nanoparticles with different sizes and their polyethylene glycol derivative. To prove high biocompatibility of obtained nanoparticles the number of in vitro toxicological tests on human fibroblasts and U251 glioblastoma cells was performed. It was shown that albumin nanoparticles' coating provides a stable and biocompatible shell and prevents cytotoxicity of magnetite core. On long exposure times (48 hours), cytotoxicity of iron oxide nanoparticles takes place due to free radical production, but this toxic effect may be neutralized by using polyethylene glycol modification.