Heptachlorepoxides: theoretical versus experimental study of the embedded samples in the matrixes of organic crystals

The analysis of heptachlorepoxides in gas- and condense phase of embedded in the organic matrixes analyte samples is highlighted. The electrospray ionization, matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS), nuclear magnetic resonance, Raman and CD spectroscopy as well as quantum chemical methods are used. The competitive formation of the variety of epoxides, strongly depending of the reaction conditions. Thus, the products of interaction of matrix-analyte matrixes under the UV–MALDI–MS experiment are comprehensively examinated. Nonetheless, that for heptachlor (HA) is known an epoxide, existing in two isomeric forms, i.e. A and B (exo- and endo-one), the study on the mechanism of the epoxidation of HA, showed formation of new epoxides C–F and an intermediate (I), characterizing with high stability, decreasing in the raw F > A > C > B > I > D > E. The epoxide D appeared enantiomer of the insecticide oxychlodran. The reported results on the pesticides, their metabolites and decomposition reactivity products contributed significantly to the field of analytical chemistry, providing possibility for elaboration of highly selective protocols for assessment of environmental contaminant issues.     

Kinetics of Absorption of Carbon Dioxide and Sulfur Dioxide in Fluorine-Containing Media

Kinetics and Catalysis - It has been established that the reactions of sulfur dioxide oxidation and carbon dioxide conversion take place in aqueous suspensions of calcium fluoride at room...     

Redox conversions of new antiviral drug Triazavirin®: electrochemical study and ESR spectroscopy

Russian Chemical Bulletin - The results of studying electrochemical conversions of 7-R-3-X-1,2,4-triazolo[5,1-c][1,2,4]-triazin-4-ones (Triazavirin® and its derivatives) using cyclic...     

An improved method for selective catalytic reduction of nitrogen oxides in exhaust gases

The selective catalytic reduction (SCR) of nitrogen dioxide in an air flow modeling the exhaust gas from an internal combustion engine is studied. Granulated V₂O₅ (13.5%)–MnO₂ (0.7–1.0%)/Al₂O₃ powder (AVK-10M catalyst) and ammonia injected into a SCR catalytic cell are used as a heterogeneous catalyst of NO₂ reduction and a reducing agent, respectively. If the efficiency of NO₂ removal is high enough and satisfies the requirements of the State Sanitary Standards for the maximum permissible concentrations of substances emitted into the atmosphere (\(MP{C_{N{O_2}}}\) = 0.085 mg/m³), the reducing agent (ammonia) is not completely consumed during SCR, so a considerable amount of NH₃ can be released into the atmosphere. Therefore, a strict control of both NO₂ and unreacted ammonia emissions is needed. The dependences of the concentrations of [NH₃] and [NO₂] on the [NH₃]/[NO₂] ratio for the model air flow passed through the AVK-10M granular heterogeneous catalyst are measured. It is found that the maximum degree of removal of NO₂ from the air takes place at [NH₃]/[NO₂] = 1.3. In the conventional process, the concentration of [NO₂] drop from 530.00 to 0.07 mg/m³, i.e., below the \(MP{C_{N{O_2}}}\). At the same time, the ammonia concentration increases to [NH₃] = 3.4 mg/m³, which becomes 85 times the \(MP{C_{N{O_2}}}\), 0.04 mg/m³. To remove unreacted ammonia from air flows, we developed [P–(SO₃ ^-)₂ · Me²⁺] sulfocationites, where Me are the Cu and/or Ca ions, P is a styrene–divinylbenzene copolymer. It is shown that the concentration of ammonia passed through the adsorption cell filled with a freshly sulfocationite drops below \(MP{C_{N{H_3}}}\) = 0.04 mg/m³. The dependences of the dynamic exchange capacity (DEC) before ammonia breakthrough for the [P–(SO₃ ^-)₂ · Cu²⁺] delta-sulfocationite on the air flow rate, [NH₃] concentration, and humidity are measured. The maximum value of the DEC, δ = 59.5 mg/cm³, is observed at an air flow velocity of 2.171 m/s, [NH₃] = 0.0035 mg/L, and 75% humidity. To illustrate practical applications of the proposed improved SCR method, it is shown that a 3-L replaceable [P–(SO₃ ^-)₂ · Cu²⁺] sorbent cartridge in a SCR exhaust gas purifier for a car internal combustion engine does not need replacement more frequently than every 50000 km.     

Effect of internal waves on intrusions in a thermocline and on upwelling

Results of the investigation into the interaction of internal waves and flows and the elaboration of a relevant mathematical model are reported. It is found in the field experiments that internal waves develop against the background of upwelling, which results in formation of jets causing intrusion velocity fluctuations. The mechanism and mathematical model of this process are proposed. A mathematical model of the suspended matter transport by jets with a wave-modulated trajectory is developed and verified.     

Preparation of Stereoregular Isotactic Poly(mandelic acid) through Organocatalytic Ring‐Opening Polymerization of a Cyclic O‐Carboxyanhydride

Poly(mandelic acid) (PMA) is an aryl analogue of poly(lactic acid) (PLA) and a biodegradable analogue of polystyrene. The preparation of stereoregular PMA was realized using a pyridine/mandelic acid adduct (Py?MA) as an organocatalyst for the ring‐opening polymerization (ROP) of the cyclic O‐carboxyanhydride (manOCA). Polymers with a narrow polydispersity index and excellent molecular‐weight control were prepared at ambient temperature. These highly isotactic chiral polymers exhibit an enhancement of the glass‐transition temperature (T_g) of 15 °C compared to the racemic polymer, suggesting potential future application as high‐performance commodity and biomedical materials.     

Metal-polymer Ag nanocomposites based on hydrophilic nitrogen- and sulfur-containing copolymers: control of nanoparticle size

Russian Chemical Bulletin - New polymer nanocomposites containing silver nanoparticles, stabilized by hydrophilic copolymers of 1-vinyl-1,2,4-triazole with vinylsulfonic acid sodium salt of...     

Intergrowth Structures of YBA2Cu3Ox Single Crystals with Oxygen Inhomogeneity

The diffraction pattern simulation of four YBa₂Cu₃O_x single crystals with inhomogeneous distribution was successfully carried out on the base of the theory of X-ray diffraction by disordered interstratified structures. The specific feature of their two-component irregular mixed-layered structures is the total segregation of layers with various oxygen content that led to the formation of so-called intergrowth structures. The concentration of admixture layers varied from 10 to 40% while oxygen content difference within the crystal ranged from 0.5 to 0.3. In one of the crystals the fluctutations of layer heights corresponded to oxygen variation from 6.2 to 7.0.     

Eu<Superscript>3+</Superscript> As a Luminescent Probe for Studying the Structure of R<Subscript>2</Subscript>O<Subscript>3</Subscript> Materials (R = Y,Eu, and Gd)

Spectra of Eu³⁺ in various dielectric matrices (Gd₂O₃:Eu³⁺, Y₂O₃:Eu³⁺, Eu₂O₃, and mSiO₂/Gd₂O₃:Eu³⁺ mesoporous particles) are studied by local cathodoluminescence. The results allowed identification of the local environment of Er³⁺ ions in amorphous samples and detection of the monoclinic Eu₂O₃ phase impurity in samples with yttrium oxide. The cathodoluminescence spectra of chemically pure Y₂O₃, Eu₂O₃, and Gd₂O₃ are recorded. Conclusions about the structural features of the materials are made and confirmed by other methods (XRD and EPMA).