The article discusses the results of a study of the effect of aqueous solution composition on the polymerization process of elemental phosphorus under the influence of accelerated electrons. Placing elemental phosphorus in water and aqueous solutions eliminates direct contact with air, thus making the process safer. In turn, adding various substances to the solution, one can control the speed and efficiency of the process. The solutions used were distilled water, degassed water, and water solutions of acetonitrile (0.01 mol·L–1), and sodium hypophosphite (1.8⋅10–5 mol·L–1). It is shown that the use of aqueous solutions of acetonitrile and sodium hypophosphite allows increasing the conversion of phosphorus by 7

This research article describes the results of studies of the processes occurring under the electron beam irradiation of elemental phosphorus in an aqueous medium. Comparisons of the results of white phosphorus samples irradiation using electron accelerators with different technical parameters are presented. The structure of the obtained phosphorus-containing polymers was determined using MALDI mass spectrometry and X-ray fluorescence analysis. A scheme of the formation of macroparticles in the process of irradiation of elemental phosphorus by a beam of accelerated electrons in an aqueous medium is discussed.

The MALDI-TOF mass-spectrometry was employed to analyze the structure of the reaction products of limonene, a natural terpene, and elemental sulfur, with the objective of identifying the occurrence of side processes, such as oxidative dehydrogenation, aromatization, and the Diels–Alder reaction cascade. The MALDI-TOF mass-spectrometry was demonstrated to be effective for the analysis of high-sulfur polymers obtained by the inverse vulcanization reaction, allowing for the unambiguous separation of sulfur-containing and hydrocarbon molecular fragments and the detailed characterization of macromolecular structures. By varying the ratio of sulfur (S8) and limonene in the initial reaction system, we were able to ascertain the limiting amount of sulfur that can be covalently bonded by terpene, as well as determine the average length of polysulfide chains under the assumption of equal reactivity and complete depletion of all double bonds. The side reaction of limonene aromatization, as indicated by the MALDI-TOF spectrum of the product resulting from its interaction with elemental sulfur, was corroborated by 1H and 13C NMR spectroscopy. Consequently, the registration and interpretation of MALDI-TOF spectra of inverse vulcanization products, either independently or in conjunction with the application of 1H and 13C NMR spectroscopy methods, as well as the determination of the limiting number of sulfur atoms that can be bound to one molecule of an unsaturated compound, paves the way for new avenues of investigation into the structure and side reactions involved in the synthesis of high-sulfur polymers.

An analysis of literature data on the set of reactions for the production of macromolecules with a high content of phosphorus and sulfur has been carried out, and basic approaches that allow the introduction of these elements into the composition of polymers and polymeric materials have been considered in compliance with the fundamental principles of green chemistry. Methods for synthesis of functional polymers under mild conditions that require minimal energy input from external sources, which can become new growth points for green industrial technologies, are considered. Particular attention focuses on the synthesis of polyphosphazenes and polyphosphoesters for biomedical purposes, as well as on the inverse vulcanization reaction to give polymers used in sorption wastewater treatment, the creation of current sources, and IR optics.

The article discusses the results of the synthesis of polymer phosphorus from the elemental phosphorus in the aqueous medium under the electron-beam irradiation. The structure of the obtained high-molecular phosphorus-containing compounds was analyzed and compared with samples of commercially available red phosphorus by mass spectrometry with matrix-activated laser desorption/ionization.

The review summarizes data on reactions with participation of the elemental cyclic form of sulfur S 8 , the key step of which is activation the eight-membered cycle S 8 by its opening under the action of various nucleophiles. This approach of involving sulfur in synthetic processes is promising from the point of view of green chemistry, as it is an alternative to the energy-intensive method of thermal treatment with the formation of sulfur diradicals. Special attention is paid to the creation of reactive systems by the reaction of elemental sulfur with dimethyl phosphate ionic liquids.

Lomonosov Moscow State University and Mendeleev University of Chemical Technology of Russia are the leading high education and research centres in the field of chemistry. Research in computational green chemistry is highly active in both institutions. The ongoing research in the Chemistry Department of Lomonosov Moscow State University covers various topics that involve combined experimental and computational studies related to green chemistry. The theoretical studies focus mainly on chemical reactions using various types of catalysts (including heterogeneous ones, nanoparticles and clusters, and industrial enzymes), photochemical processes related to the conversion of the sun energy using solar cells, and the design of novel organic compounds aiming at extracting radioactive isotopes from liquid wastes. All these studies are supported and complemented by experimental work. Mendeleev University is searching for multi-scale green-chemistry oriented bonding descriptors and applies them to the control of chemical reactions through variation of the properties of the reaction medium—an important line of development of technologies of green organic synthesis. This chapter offers an overview of the interrelated computational and green chemistry studies, highlighting their interactions and mutual benefits.

Abstract To assess the quality of atmospheric air, the authors propose to apply the process of dry deposition of impurities on an artificial underlying surface that binds impurities in contact with it. The mass of these impurities is calculated upon laboratory exposure, after being transferred to an aqueous solution. The ease of absorber fabrication and the low cost facilitate the monitoring of air pollution at various points in woodlands, where the stationary stations for air-pollution-monitoring are very difficult and costly to arrange. A large number of control points makes it possible to identify forest areas with the highest levels of air pollution. A dynamic air-quality study at one of the monitoring points is necessary and sufficient to determine the concentration of impurities. The authors surveyed an urban forest using the proposed method, and the survey results confirmed that areas with an elevated concentration of airborne nitrogen dioxide exist within the woodland. This can lead to soil eutrophication and changes in forest biodiversity at the species and ecosystem levels.

In comparison with white phosphorus, the toxicity of red phosphorus is thousands times smaller. Therefore, red phosphorus is the main modification produced and consumed by industry. Productivity, quality and product range depend on the efficiency of the technological system, on the possibility of modernizing production by introducing new progressive and environmentally friendly technologies using modern equipment. Development of a technological project for the production of red phosphorus is an urgent issue, which is the goal and the task of the research. The article presents the results of the synthesis of phosphorus-containing polymers from the white phosphorus, carried out under the influence of a beam of accelerated electrons.

The great attention paid to silver nanoparticles is largely related to their antibacterial and antiviral effects and their possible use as efficient biocidal agents. Silver nanoparticles are being widely introduced into various areas of life, including industry, medicine, and agriculture. This leads to their spreading and entering the environment, which generates the potential risk of toxic effect on humans and other biological organisms. Proposed paper describes the preparation of silver hydrosols containing spherical metal nanoparticles by photochemical reduction of Ag+ ions with oxalate ions. In deaerated solutions, this gives ~10 nm particles, while in aerated solutions, ~20 nm particles with inclusion of the oxide Ag2O are obtained. Nanoparticles inhibit the bacterium Escherichia coli and suppress the cell growth at concentrations of ~1 × 10−6–1 × 10−4 mol L−1. Silver particles cause the loss of pili and deformation and destruction of cell membranes. A mechanism of antibacterial action was proposed, taking into account indirect suppressing action of Ag+ ions released upon the oxidative metal dissolution and direct (contact) action of nanoparticles on bacterial cells, resulting in a change in the shape and destruction of the bacteria.

The comparative stability of ionic liquids containing alkyl-substituted imidazolium and phosphonium cations on exposure to gamma radiation (60Co source) under the same conditions has been studied for the first time. It has been shown that when exposed to 60Co gamma radiation (an absorbed dose of up to 550 kGy) in the presence of air oxygen, phosphonium and imidazolium ionic liquids exhibit high radiolytic stability. Under these conditions, the yield of radiolytic products is no more than 1 wt %. At the same time, in contrast to phosphonium ionic liquids, imidazolium ionic liquids undergo radiolytic staining at absorbed doses in the range studied. Based on IR, UV, and 1H NMR spectroscopy and known literature data, an assumption has been made about the most probable mechanisms of transformation of imidazolium cations of an ionic liquid under the influence of gamma radiation.

The aim of the study is to search for a reaction that provides the possibility of tandem “one-pot” formation of polymer networks during radical copolymerization of N-vinyl-2-pyrrolidone and glycidyl methacrylate. It was shown that the addition of recently synthesized 1,3-dimethylimidazolium (phosphonooxy-)oligosulfanide makes it possible to obtain a cross-linked copolymer in one stage as a result of radical copolymerization of N-vinyl-2-pyrrolidone and glycidyl methacrylate with a molar ratio of monomers less than 1.4. The structure of the copolymerization products of N-vinyl-2-pyrroldione and glycidyl methacrylate formed in the presence of 1,3-dimethylimidazolium (phosphonooxy-)oligosulfanide was characterized by 1H NMR, FTIR and MALDI spectroscopy. 1H NMR spectroscopy revealed an interaction under moderate heating between glycidyl methacrylate and 1,3-dimethylimidazolium (phosphonooxy-)oligosulfanide, accompanied by the formation of a mixture of unsaturated products of complex structure, presumably acting as crosslinking agents. It is shown that when the molar ratio of N-vinyl-2-pyrroldione/glycidyl methacrylate comonomers is 0.89, a densely crosslinked copolymer is formed, capable of limited swelling in water with a velocity constant of 5.06 × 10−2 min−1 and an equilibrium degree of swelling of about 227%.

The effect of an increase in the electron density in silver nanoparticles during their formation through photochemical reduction of Ag+ ions in the presence of oxalate has been discovered and substantiated. The effect causes a shift of the of localized surface plasmon resonance (SPR) band from 402 to 383 nm and a decrease in its width. The quantitative relationship between the band shift value and electron density has been revealed. The observed shift of 19 nm corresponds to an approximately 10% increase in the electron concentration in nanoparticles. The observed is possibly common for other metals and affects the performance of various catalytic reactions involving metals in the nanoscale state.

Abstract The opening of the S8 ring with the formation of linear sulfur oligomers in the presence of tri-n-butylmethylphosphonium dimethylphosphate is shown. The reaction products are separated and characterized with 1H, 13C, 31P, 17O NMR spectroscopy, HD-MS, MALDI spectroscopy and XRD. It is shown that dimethylphosphate-anion is active in the reaction, and the addition of sulfur atoms occurs via the oxygen atom of dimethylphosphate-anion. It is found that a mixture of products is formed, which differ in the number of sulfur atoms in the chain. The assumptions were made about the mechanism of interaction of sulfur with tri-n-butylmethylphosphonium dimethylphosphate.

The review considers the current ideas of a relatively new field of "green chemistry" in the field of chemical processing of renewable natural plant raw materials. For a number of processes, the ways, methods and some technological aspects of obtaining new compounds and reagent systems, biodegradable compositions and "green chemistry" products that are in demand in various sectors of the economy, industry and life support of society are shown. The article presents the results of the analysis of Russian and world reserves of forest resources according to authoritative modern sources and proposals for their conservation and restoration. The problems of biorefiling of plant raw materials are described, one of which is the valorization of lignin-the aromatic component of the chemical composition of wood. It is proposed to obtain biodegradable systems and compositions based on the by-product of wood processing lignosulfonate of a neutral production method characterized by a high content of polysaccharides in the hemicellulose of the carbohydrate part of wood after the separation of cellulose. The ways of using modified cellulose products as inhibitors of salt deposition and gas hydrate formation, and the areas of their application in oilfield chemistry are shown. Lignin and other components of plant resources have long been the basis of various classes of fibers of natural origin, including plant and animal origin, artificial fibers. In the sector of creating materials with new properties that have a wide range of practical applications, the review describes the production of PLA polylactide synthesized from lactic acid as a modern alternative to many synthetic polymers obtained from refined petroleum products. For the products of the interaction of ammonium lactate and n-butyl alcohol, a kinetic model for the production of butyl lactate, an intermediate product of green chemistry, is described. The results of the study of a specific class of compounds - ionic liquids - traditionally considered as so-called "green solvents" are presented. An approach to the creation of a mathematical model by calculating the adsorption characteristics for evaluating the effectiveness of systems and composites based on biodegradable polymers in the direction of "green chemistry" is proposed.

The electron density of a nanoparticle is a very important characteristic of the properties of a material. This paper describes the formation of silver nanoparticles (NPs) and the variation in the electronic state of an NP’s surface upon the reduction in Ag+ ions with oxalate ions, induced by UV irradiation. The calculations were based on optical spectrophotometry data. The NPs were characterized using Transmission electron microscopy and Dynamic light scattering. As ~10 nm nanoparticles are formed, the localized surface plasmon resonance (LSPR) band increases in intensity, decreases in width, and shifts to the UV region from 402 to 383 nm. The interband transitions (IBT) band (≤250 nm) increases in intensity, with the band shape and position remaining unchanged. The change in the shape and position of the LSPR band of silver nanoparticles in the course of their formation is attributable to an increasing concentration of free electrons in the particles as a result of a reduction in Ag+ ions on the surface and electron injection by CO2− radicals. The ζ-potential of colloids increases with an increase in electron density in silver nuclei. A quantitative relationship between this shift and electron density on the surface was derived on the basis of the Mie–Drude theory. The observed blue shift (19 nm) corresponds to an approximately 10% increase in the concentration of electrons in silver nanoparticles.

The synthesis of polymers using elemental sulphur as a chemical agent has been studied in relation to the worldwide overproduction of cyclo-octasulphur. Herein, the mechanisms of the processes leading to the inclusion of elemental sulphur into macromolecules have been reviewed and the main methods for reduction of the reaction temperature required for the S8 ring opening have been shown. Approaches to the activation of cyclo-octasulphur in the synthesis and macromolecule cross-linking reactions were discussed in the context of finding the chemical agents and conditions that satisfy the principles of green chemistry.

The new initiator of the polymerization of acrylamide, leading to the formation of crosslinked polyacrylamide, was discovered. The structure of the synthesized polyacrylamide was characterized by XRD, 1H NMR, and 13C NMR spectroscopy. It was shown that 1,3-dimethylimidazolium (phosphonooxy-)oligosulphanide is able to initiate radical polymerization under drying aqueous solutions of acrylamide, even at room temperature. According to XRF data, the synthesized polyacrylamide gel contains 0.28 wt% of sulphur. The formed polymer network has a low crosslinking density and a high equilibrium degree of swelling. The swelling rate of polyacrylamide gel in water corresponds to the first order kinetic equation with the rate constant 6.2 × 10−2 min−1. The initiator is promising for combining acrylamide polymerization with the processes of gel molding and drying.

Interaction of 1,3-dimethylimidazolium dimethylphosphate and elemental sulfur synthesized a new initiator of polymerization of formaldehyde, opening the possibility of its implementation in accordance with the principles of Green chemistry. The possibility of fast oligomerization of formaldehyde in an aqueous medium with the formation of insoluble products, the structure of which is determined by FTIR, MALDI-TOF, 1H NMR, 13C NMR, HSQC and HMBC spectroscopy, is shown. It was found that (phosphonooxy-)oligosulfanide anion initiates formaldehyde oligomerization by anionic mechanism with chain termination due to interaction with water. It was shown that the synthesized formaldehyde oligomers retain resistance to degradation up to a temperature of 443 K, and then slowly thermally decompose to a temperature of 513 K, above which the rate of thermal degradation increases significantly.