Oxidative Aromatization of 4,7-Dihydro-6-nitroazolo[1,5-a]pyrimidines: Synthetic Possibilities and Limitations, Mechanism of Destruction, and the Theoretical and Experimental Substantiation.

The reaction tolerance of the multicomponent process between 3-aminoazoles, 1-morpholino-2-nitroalkenes, and aldehydes was studied. The main patterns of this reaction have been established. Conditions for the oxidation of 4,7-dihydro-6-nitroazolo[1,5-a]pyrimidines were selected. Previous claims that the 4,7-dihydro-6-nitroazolo[1,5-a]pyrimidines could not be aromatised have now been refuted. Compounds with an electron-donor substituent at position seven undergo decomposition during oxidation. The phenomenon was explained based on experimental data, electro-chemical experiment, and quantum-chemical calculation. The mechanism of oxidative degradation has been proposed.

Effect of Aryl-, Halogen-, and Ms-Aza-Substitution on the Luminescent Properties and Photostability of Difluoroborates of 2,2'-Dipyrrometenes.

Boron(III) complexes with alkyl-, phenyl-, and halogen-substituted 2,2'-dipyrromethenes (BODIPY) and meso-aza-dipyrrometenes (ms-aza-BODIPY) were synthesized. The structure relationship of the obtained coordination compounds with their luminescent characteristics is analyzed. Arylated BODIPY, in contrast to alkyl-substituted analogs, is more sensitive to interparticle interactions with a solvent, causing a decrease in the quantum yield by up to 40%. The introduction of phenyl substituents into the BODIPY molecule shifts the first absorption band bathochromic, significantly (32-37 nm) increases the Stokes shift in the emission spectrum, but reduces the probability of the S0 → S1 electronic transition as compared to alkylated complexes. Replacing the methine carbon atom with nitrogen leads to quenching of ms-aza-BODIPY fluorescence compared to BODIPY up to 5-20%. The stability of 2,2'-dipyrromethenes difluoroborates to oxidative destruction under the influence of UV irradiation in cyclohexane solutions was evaluated. It has been shown that symmetric aryl substitution in pyrrole cycles of dipyrromethene significantly increases the photostability of the corresponding compounds as compared to alkyl-substituted analogs and is an effective method of obtaining boron (III) dipyrromethenates with practically useful properties. It has been established that the replacement of the methin ms-spacer of dipyrromethene by a nitrogen atom significantly reduces the photostability of ms-aza-dipyrromethenates of boron. Halogenation of ß-positions of pyrrole cycles by a factor of 5-8 reduces the photostability of difluoroborates ms-aza-dipyrromethenes in comparison with a non-halogenated analogue.

Effect of oil pollution on the ecological condition of soils and bottom sediments of the arctic region (Yakutia).

Oil and petroleum products are known to be among the most widespread soil pollutants. The risk of emergencies is sure to increase greatly in conditions of abnormally low temperatures. Oil and oil products are not only toxic to the environment, but can also have a negative impact on the state of the permafrost zone, accelerating the processes of permafrost degradation. The goal of the research was to study the soils and bottom sediments for oil pollution in the Arctic region of Yakutia. The research was carried out with using the complex of geochemical and microbiological methods of analysis. It had shown that at present oil pollution was mainly concentrated on the objects bearing a high technogenic load. However, some migration of hydrocarbons was observed with melt, seasonal melt and rainwaters, as a result of which the natural background of the nearby territories became technogenic character. In the Arctic conditions for the first time according to the obtained data on geochemical and microbiological studies oxidative destruction of oil pollutants in soil occurred mainly under the influence of physic and chemical environmental factors, not by microbial oxidation. Sluggish processes of mineralization of organic residues and the transformation of oil pollutants by the type of putrefaction led to the colonization of oil-polluted soils of the Arctic with putrefying and pathogenic microorganisms. The purpose of further research will be studying the possibility of intensification of soil remediation processes of technologically disturbed soils at abnormally low temperatures.

Air ionization as a control technology for off-gas emissions of volatile organic compounds.

High energy electron-impact ionizers have found applications mainly in industry to reduce off-gas emissions from waste gas streams at low cost and high efficiency because of their ability to oxidize many airborne organic pollutants (e.g., volatile organic compounds (VOCs)) to CO2 and H2O. Applications of air ionizers in indoor air quality management are limited due to poor removal efficiency and production of noxious side products, e.g., ozone (O3). In this paper, we provide a critical evaluation of the pollutant removal performance of air ionizing system through comprehensive review of the literature. In particular, we focus on removal of VOCs and odorants. We also discuss the generation of unwanted air ionization byproducts such as O3, NOx, and VOC oxidation intermediates that limit the use of air-ionizers in indoor air quality management.

Copper-catalyzed activation of molecular oxygen for oxidative destruction of acetaminophen: The mechanism and superoxide-mediated cycling of copper species.

In this study, the commercial zero-valent copper (ZVC) was investigated to activate the molecular oxygen (O2) for the degradation of acetaminophen (ACT). 50 mg/L ACT could be completely decomposed within 4 h in the ZVC/air system at initial pH 3.0. The H2O2, hydroxyl radical (OH) and superoxide anion radical (O2-) were identified as the main reactive oxygen species (ROSs) generated in the above reaction; however, only OH caused the decomposition and mineralization of ACT in the copper-catalyzed O2 activation process. In addition, the in-situ generated Cu+ from ZVC dissolution not only activated O2 to produce H2O2, but also initiated the decomposition of H2O2 to generate OH. Meanwhile, the H2O2 could also be partly decomposed into O2-, which served as a mediator for copper cycling by reduction of Cu2+ to Cu+ in the ZVC/air system. Therefore, OH could be continuously generated; and then ACT was effectively degraded. Additionally, the effect of solution pH and the dosage of ZVC were also investigated. As a result, this study indicated the key behavior of the O2- during Cu-catalyzed activation of O2, which further improved the understanding of O2 activation mechanism by zero-valent metals.