Structure and conductivity of yttria and scandia‐doped zirconia crystals grown by skull melting

In this paper a detailed study of the (ZrO₂)_1‐x(Y₂O₃)_x (x=0.025–0.15), (ZrO₂)_1‐x(Sc₂O₃)_x (x = 0.06 – 0.11) and (ZrO₂)_1‐x‐y(Sc₂O₃)_x(Y₂O₃)_y (x=0.07 – 0.11; y=0.01 – 0.04) solid solution crystals grown by skull melting technique is presented. The structure, phase composition, and ion conductivity of the obtained crystals were investigated by X‐ray diffraction, transmission electron microscopy, Raman scattering spectroscopy, and impedance spectroscopy. Maximum conductivity as (ZrO₂)_1‐x(Y₂O₃)_x and (ZrO₂)_1‐x(Sc₂O₃)_x solid solution crystals is observed for the compositions containing 10 mol% stabilizing oxide, and the conductivity of 10ScSZ is ~3 times higher than for 10YSZ. Experiments on crystal growth (ZrO₂)_1‐x‐y(Sc₂O₃)_x(Y₂O₃)_y solid solutions showed that uniform, transparent crystals 7Sc3YSZ, 7Sc4YSZ, 8Sc2YSZ, 8Sc3YSZ, 9Sc2YSZ, 9Sc3YSZ, 10Sc1YSZ, and 10Sc2YSZ are single phase crystal containing t″ phase. It is established that a necessary condition of melt growth of (ZrO₂)_1‐x‐y(Sc₂O₃)_x(Y₂O₃)_y single‐phase crystals is the total concentration of the stabilizing oxides from 10 to 12 mol%. The addition of Y₂O₃ affects the (ZrO₂)_1‐x‐y(Sc₂O₃)_x(Y₂O₃)_y solid solution conductivity different ways and depends on the Sc₂O₃ content in the starting composition. The effects of structure, phase composition, concentration, and type of stabilizing oxides on the electrical characteristics of obtained crystals are discussed.     

Kinetics of phase formation in the Ln–O–S (Ln=La,Gd, Y) systems during oxide sulfidation in ammonium thiocyanate vapor

Kinetics and mechanism of phase formation in the Ln–O–S (Ln=La, Gd, Y) systems during Ln₂O₃ sulfidation in ammonium thiocyanate vapor and the identified sequence of transformations of obtained phases in the temperature range 873‐1273 K have been studied. The kinetic dependencies for the reactions involved were fitted by the Jander equation for topochemical heterogeneous reactions with a squared correlation coefficient R²=.99. The reaction rate constants, pre‐exponential factors, and effective activation energies for the reaction formation of compounds have been calculated, and approximate times and low temperatures for the formation of particular phases have been found.     

DNA-based materials as chemical reactors for synthesis of metal nanoparticles

In this minireview we highlight a recent progress in preparation of DNA-based matrices that can be used as reactors for templating of inorganic nanomaterials and, in particular, highlight catalytic applications of such hybrid materials. We also discuss advantages and disadvantages of DNA utilization as a material and outline prospects of DNA-based technologies in future.     

Synthesis of trimethylolpropane esters of tall oil fatty acids and properties of polyurethane coatings on their basis

Tall oil fatty acids (TOFA) were esterified with trimethylolpropane (TMP) without a catalyst at different molar ratios of TMP to TOFA. A molar ratio was defined, at which a polyol stable in long-term storage, with the maximum content of TMP monoesters, was synthesized. Fourier transform infrared spectroscopy and gas chromatography were used for the identification of the polyols’ chemical structure and composition. Based on the synthesized polyols, polyurethane coatings were prepared. The effect of the isocyanate index and concentration of traditional Sn-based and less toxic Bi-based catalysts on the gel time of the polyurethane composition, and the mechanical and thermal properties of the coatings was studied. It was found that the new coatings had high tensile strength and modulus of elasticity, comparable with the strength and modulus of the polyurethane based on diethanolamides of TOFA. The initial temperature of decomposition of these coatings was higher than that of the polyurethanes based on esters of TOFA and a number of uralkyds. The coatings based on TMP esters of TOFA were obtained without the use of solvents, and potentially, these esters can be used in spray-applied VOC-free polyurethane coatings’ formulation.     

On the mechanisms of secondary flows in a gas vortex unit

The hydrodynamics of secondary flow phenomena in a disc‐shaped gas vortex unit (GVU) is investigated using experimentally validated numerical simulations. The simulation using ANSYS FLUENT^® v.14a reveals the development of a backflow region along the core of the central gas exhaust, and of a counterflow multivortex region in the bulk of the disc part of the unit. Under the tested conditions, the GVU flow is found to be highly spiraling in nature. Secondary flow phenomena develop as swirl becomes stronger. The backflow region develops first via the swirl‐decay mechanism in the exhaust line. Near‐wall jet formation in the boundary layers near the GVU end‐walls eventually results in flow reversal in the bulk of the unit. When the jets grow stronger the counterflow becomes multivortex. The simulation results are validated with experimental data obtained from Stereoscopic Particle Image Velocimetry and surface oil visualization measurements. © 2018 The Authors AIChE Journal published by Wiley Periodicals, Inc. on behalf of American Institute of Chemical Engineers AIChE J, 64: 1859–1873, 2018     

Monodisperse Metal Nanoparticle Catalysts: Synthesis, Characterizations, and Molecular Studies Under Reaction Conditions

We aim to develop novel catalysts that exhibit high activity, selectivity and stability under real catalytic conditions. In the recent decades, the fast development of nanoscience and nanotechnology has allowed synthesis of nanoparticles with well-defined size, shape and composition using colloidal methods. Utilization of mesoporous oxide supports effectively prevents the nanoparticles from aggregating at high temperatures and high pressures. Nanoparticles of less than 2?nm sizes were found to show unique activity and selectivity during reactions, which was due to the special surface electronic structure and atomic arrangements that are present at small particle surfaces. While oxide support materials are employed to stabilize metal nanoparticles under working conditions, the supports are also known to strongly interact with the metals through encapsulation, adsorbate spillover, and charge transfer. These factors change the catalytic performance of the metal catalysts as well as the conductivity of oxides. The employment of new in situ techniques, mainly high-pressure scanning tunneling microscopy (HPSTM) and ambient-pressure X-ray photoelectron spectroscopy (APXPS) allows the determination of the surface structure and chemical states under reaction conditions. HPSTM has identified the importance of both adsorbate mobility to catalytic turnovers and the metal substrate reconstruction driven by gaseous reactants such as CO and O₂. APXPS is able to monitor both reacting species at catalyst surfaces and the oxidation state of the catalyst while it is being exposed to gases. The surface composition of bimetallic nanoparticles depends on whether the catalysts are under oxidizing or reducing conditions, which is further correlated with the catalysis by the bimetallic catalytic systems. The product selectivity in multipath reactions correlates with the size and shape of monodisperse metal nanoparticle catalysts in structure sensitive reactions.     

Flavonoid Metabolites in the Hemolymph of European Pine Sawfly (Neodiprion sertifer) Larvae

Flavonoids in the hemolymph of European pine sawfly (Neodiprion sertifer) larvae that were feeding on Pinus sylvestris needles were identified. HPLC-ESI-MS analysis revealed that the main components in the hemolymph were flavonol di- and triglucosides and a catechin monoglucoside. These compounds were isolated from the larval hemolymph and their structures were established by HPLC-MS, GC-MS, and NMR spectroscopy. The isolated flavonoids were identified as (+)-catechin 7-O-β-glucoside, isorhamnetin 3,7,4'-tri-O-β-glucoside, kaempferol 3,7,4'-tri-O-β-glucoside, and quercetin 3,7,4'-tri-O-β-glucoside. The combined concentration of these four compounds in the hemolymph was 3.7 mg/ml. None of these compounds was present in the needles of P. sylvestris. Therefore, we propose that the flavonoid glucosides were produced by the larvae from flavonoid monoglucosides and (+)-catechin obtained from the pine needles.     

Morphology and adsorption properties of chemically modified MWCNT probed by nitrogen,n-propane and water vapor

The poor compatibility of carbon materials with different dispersion media can be overcome by surface functionalization. In this work, multiwall carbon nanotubes (MWCNTs) were doped by oxygen and nitrogen at low concentrations. Morphological and structural changes caused by chemical treatment were monitored using nitrogen, propane and water vapor adsorption measurements. Pore size distribution (PSD) functions derived from various models are compared. The contribution of slit-shaped pores to the total surface area available for adsorbed molecules is smaller than that of cylindrical pores. Functionalities with heteroatoms (both O and N) enhance water adsorption onto MWCNTs. However, no statistical difference is observed between the water adsorption properties of O- or N-containing MWCNTs.     

Peroxidase-catalyzed oxidation of β-carotene in HL-60 cells and in model systems: Involvement of phenoxyl radicals

Recent studies provide extensive evidence for the importance of carotenoids in protecting against oxidative stress associated with a number of diseases. In particular, reactions of carotenoids with phenoxyl radicals generated by peroxidasecatalyzed one-electron metabolism of phenolic compounds may represent an important antioxidant function of carotenoids. To further our understanding of the antioxidant mechanisms of carotenoids, we used in the present work two different phenolic compounds, phenol and a polar homologue of vitamin E (2,2,5,7,8-pentamethyl-6-hydroxychromane, PMC), as representatives of two different types of phenols to study reactions of their respective phenoxyl radicals with carotenoids in cells and in model systems. We found that phenoxyl radicals of PMC did not oxidize β-carotene in either HL-60 cells or in model systems with horseradish peroxidase (HRP)/H₂O₂. In contrast, the phenoxyl radicals generated from phenol (by native myeloperoxidase in HL-60 cells or HRP/H₂O₂ in model systems) effectively oxidized β-carotene and other carotenoids (canthaxanthin, lutein, lycopene). One-electron reduction of the phenoxyl radical by ascorbate (assayed by electron spin resonance-detectable formation of semidehydroascorbyl radicals) prevented HRP/H₂O₂-induced oxidation of β-carotene. PMC, but not phenol, protected β-carotene against oxidation induced by a lipid-soluble azo-initiator of peroxyl radicals. No adducts of peroxidase/phenol/H₂O₂-induced β-carotene oxidation intermediates with phenol were detected by high-performance liquid chromatography-mass spectrometry analysis of the reaction mixture. Since carotenoids are essential constituents of the antioxidant defenses in cells and biological fluids, their depletion through the reaction with phenoxyl radicals formed from endogenous, nutritional and environmental phenolics, as well as phenolic drugs, may be an important factor in the development of oxidative stress.     

Exchange reactions control for selective separation of glyoxylic acid in technological mixtures of glyoxal oxidation

Separation of glyoxylic acid from unpurified multicomponent technological mixtures, resulting in the process of direct oxidation of glyoxal, and preparation of sodium glyoxylate are developed. The mixtures are treated with an optimal amount of CaCO_3, which has to be prespecified by acidic–basic titration of the technological mixtures. Both separation of glyoxylic acid and preparation of sodium glyoxylate take place owing to ionic exchange reactions: calcium glyoxylate is easily converted into glyoxylic acid by action of oxalic acid. Reaction with Na₂CO₃ leads to the formation of sodium glyoxylate.