Ozonation of Decalin as a Model Saturated Cyclic Molecule: A Spectroscopic Study.

Ozonolysis is used for oxidation of a model cyclic molecule-decalin, which may be considered as an analog of saturated cyclic molecules present in heavy oil. The conversion of decalin exceeds 50% with the highest yield of formation of acids about 15-17%. Carboxylic acids, ketones/aldehydes, and alcohols are produced as intermediate products. The methods of UV-visible, transmission IR, attenuated total reflection IR-spectroscopy, NMR and mass-spectrometry were used to identify reaction products and unravel a possible reaction mechanism. The key stage of the process is undoubtedly the activation of the first C-H bond and the formation of peroxide radicals.

Microwave-Assisted Synthesis of Water-Dispersible Humate-Coated Magnetite Nanoparticles: Relation of Coating Process Parameters to the Properties of Nanoparticles.

Nowadays, there is a demand in the production of nontoxic multifunctional magnetic materials possessing both high colloidal stability in water solutions and high magnetization. In this work, a series of water-dispersible natural humate-polyanion coated superparamagnetic magnetite nanoparticles has been synthesized via microwave-assisted synthesis without the use of inert atmosphere. An impact of a biocompatible humate-anion as a coating agent on the structural and physical properties of nanoparticles has been established. The injection of humate-polyanion at various synthesis stages leads to differences in the physical properties of the obtained nanomaterials. Depending on the synthesis protocol, nanoparticles are characterized by improved monodispersity, smaller crystallite and grain size (up to 8.2 nm), a shift in the point of zero charge (6.4 pH), enhanced colloidal stability in model solutions, and enhanced magnetization (80 emu g-1).

The Green Method in Water Management: Electron Beam Treatment.

During the prebiotic era, radiolytic transformations in the oceans played a key role in purifying water from toxic impurities and, thus, played a role in the formation of the aquatic environment of our planet, making it suitable for the emergence of life. Today, the planet again faces the challenge of how to provide people with clean water. Therefore, it is reasonable to look back at past historical stages and again consider the possibility of neutralizing pollutants in water by means of radiolysis, which has already been tested by time. Modern radiolytic treatments can be much faster and safer thanks to the advent of powerful electron accelerators and high-rate electron beam treatment (ELT) of water and wastewater. Radiolytic treatment of water using accelerated electrons corresponds to the essence of advanced oxidative technologies and green chemistry. The ELT of water instantly generates a high concentration of short-lived radicals that can quickly neutralize and decompose chemical and bacterial pollutants. Due to the ability of accelerated electrons to penetrate into a substance, ELT provides the decomposition of both dissolved and suspended pollutants. The cleaning effect of ELT is due to the ability to inactivate toxic and chromophore functional groups, transform impurities into an easily removable form, damage the DNA of microorganisms and their spore forms, and increase the biodegradability of organic impurities. The use of ELT in water treatment provides significant savings in chemical reagents, thereby improving quality and reducing the number of cleaning steps. The compactness, high degree of automation of the equipment used, energy efficiency, high productivity, and excellent compatibility with traditional water treatment methods are important advantages of ELT. Unlike conventional chemicals, the excess radicals generated in the ELT process are converted back to water and hydrogen; thus, the chemical and corrosive activity of water does not increase. Equipping research institutes with electron accelerators, developing cheaper accelerators, and granting government support for pilot projects are key conditions for introducing ELT into water treatment practice.

Spectrophotometric determination of ozone in solutions: Molar absorption coefficient in the visible region.

A new approach for the determination of ozone concentration in solutions in organic liquids based on spectrophotometric absorbance measurements in the visible region was proposed and substantiated. The molar absorption coefficient of ozone in the absorption maximum at ~600nm is 8.0mol-1 L cm-1 for hydrocarbons (hexane, heptane, isooctane), CHCl3 and CCl4, and 5.3mol-1 L cm-1 for methanol and 4.5mol-1 L cm-1 for water (±10%). The coefficient monotonically decreases with increasing dielectric constant of the liquid. The low molar absorption coefficient allows the use of spectrophotometric measurements for determination of high ozone concentrations ranging from approximately 1·10-2mol L-1 up to 1.0mol L-1.

Ecotoxicity of different-shaped silver nanoparticles: Case of zebrafish embryos.

As the worldwide application of silver nanomaterials in commercial products increases every year, and concern about the environmental risks of such nanoparticles also grows. A clear understanding of how different characteristics of nanoparticles contribute in their toxic behavior to organisms are imperative for predicting and control nanotoxicity. Within our research, we investigated the toxic effect of two types of silver nanoparticles (spherical and flat Ag nanoparticles) on zebrafish (Danio rerio) embryos. Particular interest was paid to proper characterization of Ag nanoparticles initially and during the experiment. A proper test medium was found and used for ecotoxicity evaluation. The behavior of flat silver nanoparticles with respect to embryos of zebrafish was analyzed and compared to the ecotoxicity of silver ionic form (AgNO3). Both types of nanoparticles showed a more pronounced toxic effect to Danio rerio embryos than silver ions (AgNO3), while silver nanoplates were more harmful than Ag nanospheres. While previous investigations showed that toxicity of Ag nanoparticles can be explained by the presence of Ag+ in solution of silver nanoparticles, our results demonstrate that the harmful effects of nanosilver may be associated with silver nanoparticles themselves than with ionic silver released into solution.

Chemical and spectral behavior of nitric acid in aqueous sulfuric acid solutions: Absorption spectrum and molar absorption coefficient of nitronium ion.

The chemical species formed from nitric acid in aqueous solutions of sulfuric acid (up to 18.0molL-1) were studied by optical spectroscopy method. The concentration region of nitronium ion formation was identified and NO2+ ion absorption spectrum was measured (λmax≤190nm and ε190=1040±50mol-1Lcm-1).

Adsorption of ozone and plasmonic properties of gold hydrosol: the effect of the nanoparticle size.

The impact of the size of gold nanoparticles on the magnitude of the bathochromic shift of their plasmon resonance peak upon ozone adsorption is revealed and analyzed. Namely, the plasmon band position of 7, 10, 14 and 32 nm nanoparticles shifts toward longer wavelengths by 51, 35, 23 and 9 nm respectively, i.e. the smaller the nanoparticles, the greater the shift of the band. Thus, the sensor efficiency of gold hydrosol increases with a decrease in the nanoparticle size. The shift of the Fermi level is a linear function of the inverse radius of nanoparticles. The observed alterations in the gold nanoparticle plasmonic properties and the Fermi level position are explained by a decrease in the electron density of nanoparticles caused by the electrons' partial binding by adsorbed O3 molecules. The insignificance of oxygen and nitrous oxide effects on plasmonic properties of gold hydrosol is observed.

Radiation-induced high-temperature conversion of cellulose.

Thermal decomposition of cellulose can be upgraded by means of an electron-beam irradiation to produce valuable organic products via chain mechanisms. The samples being irradiated decompose effectively at temperatures below the threshold of pyrolysis inception. Cellulose decomposition resembles local "explosion" of the glucopyranose unit when fast elimination of carbon dioxide and water precede formation of residual carbonyl or carboxyl compounds. The dry distillation being performed during an irradiation gives a liquid condensate where furfural and its derivatives are dominant components. Excessively fast heating is adverse, as it results in a decrease of the yield of key organic products because pyrolysis predominates over the radiolytic-controlled decomposition of feedstock. Most likely, conversion of cellulose starts via radiolytic formation of macroradicals do not conform with each other, resulting in instability of the macroradical. As a consequence, glucosidic bond cleavage, elimination of light fragments (water, carbon oxides, formaldehyde, etc.) and formation of furfural take place.