Model Calculations and Experimental Studies as a Route Toward Simplification of the Kinetic Mechanism of the H2O2–NaSCN–NaOH–CuSO4 Homogeneous Oscillator

Oscillatory chemical reactions are usually characterized by complicated kinetic mechanisms in which the source of instability is combined with the parallel dissipative process. One of such systems is the H₂O₂–NaSCN–NaOH–CuSO₄ homogeneous oscillator, in which dynamic instabilities are associated with the irreversible oxidation of thiocyanate ions with hydrogen peroxide. Following our previous studies on this system, we now propose further intuitive and substantial simplification of its kinetic mechanism toward the scheme involving only five intermediates. Its compatibility with our previous, nine‐variable model is verified in terms of model calculations, compared with experimental potentiometric and spectrophotometric data. In particular, supercritical nature of a Hopf bifurcation as a route toward oscillations born out of a single steady state upon increasing catalyst (copper species) concentration was observed in the model and an analogous type of bifurcation is suggested by available experimental data. Our work is a step toward final reduction of the mechanism of the studied system to the “minimum oscillator,” the concept used earlier, e.g., for the Belousov–Zhabotinsky reaction, of however remarkably different kinetic mechanism.     

Properties of carbon-based structures synthesized in nuclear reactions induced by bremsstrahlung γ quanta with threshold energy of 10 MeV at helium pressure of 1.1 kbar

Helium gas with an initial pressure of about 1.1 kbar inside a high-pressure chamber (HeHPC) has been irradiated by bremsstrahlung γ quanta with a threshold energy of 10 MeV for 1.0 × 10⁵ s produced by an electron-beam current of 22–24 μA. After opening the HeHPC, the residual pressure of helium is equal to 430 bar. Synthesized black foils with a variety of other objects are found inside the HeHPC. They are located on the inner surfaces of the reaction chamber made of high-purity copper (99.99%), the entrance the window of γ quanta made of beryllium bronze and a copper container of nuclear and chemical reaction products. Elemental analysis with the use of scanning electron microscopy and X-ray microprobe analysis has revealed that the foils contain predominantly carbon and small quantities of other elements from carbon to iron. The results are in good agreement with the cycle of investigations of the authors devoted to the γ-quanta irradiation of dense hydrogen and helium gases in the presence (absence) of metals in a reaction chamber.     

Influence of Copper(II) Ions on Radicals in DOPA–Melanin

DOPA–melanin (DOPA = 3,4-dihydroxyphenyl-alanine) complexes with Cu(II) cations were studied by electron paramagnetic resonance (EPR) spectroscopy. After the addition of metal cations to the melanin polymer, the EPR spectra parameters were measured. The axial g-factor values are g _|| = 2.20 and g _^ = 2.0 5 g_{ \bot } = 2.0 5 . Since $ g_{||} > g_{ \bot } > 2 $ g_{||} > g_{ \bot } > 2 , the ground state orbital of the unpaired electron of the Cu(II) complex is | x ²  -   y ² ñ \left| {{{x}}^{ 2} } \right. \, - \, \left. {{{y}}^{ 2} } \right\rangle . Square coordination of these cations in melanin is proposed. The influence of the Cu(II) concentration in solution used during synthesis on the concentration of melanin radicals was investigated. Cu(II) cations causes the decrease in the paramagnetic center concentration in melanin. The Cu(II) EPR spectra are not saturated within the microwave power range of 0.7–70 mW used in our experiment.     

Modification of Surface Properties of Colloidal Suspensions of NixOy-SiO2 Mixed Oxides with Different Ni Contents by the Adsorption Layers of Poly(Vinyl Alcohol)

Journal of Cluster Science - The adsorption and electrokinetic properties of hybrid silica materials composed of nickel and silicon oxides (NixOy-SiO2), characterized by different contents of...     

Vinyl Acetate Copolymers in Die Pressing of Alumina

The studies on the application of the emulsions of poly(vinyl acetate-co-allyl ether)s containing nonionic hydrophilic poly(oxyethylene) fragments as binders in the die pressing of alumina is presented. It was found that introduction of hydrophilic fragments into molecules of a typical water dispersible polymer led to better polymer affinity to the ceramic powders. It was also shown that low molecular mass of such copolymers should be relatively low ca 1500 g mol^–1 to increase the density and thickening uniformity of the samples before and after sintering. The resultant sinters indicated exceptionally high mechanical strength (bending strength ca 500 MPa). This revised version was published online in August 2006 with corrections to the Cover Date.     

Heteronuclear recoupling in solid-state magic-angle-spinning NMR via overtone irradiation

A heteronuclear dipolar recoupling scheme applicable to I-S spin pairs undergoing magic-angle-spinning (MAS) is introduced, based on the overtone irradiation of one of the coupled nuclei. It is shown that when I is a quadrupole, for instance (14)N, irradiating this spin at a multiple of its Larmor frequency prevents the formation of MAS dipolar echoes. The ensuing S-spin signal dephasing is significant and dependent on a number of parameters, including the I-S dipolar coupling, the magnitude of I's quadrupolar coupling, and the relative orientations between these two coupling tensors. When applied to a spin-1 nucleus, this overtone recoupling method differs from hitherto proposed recoupling strategies in that it involves only the +/-1> I(z) eigenstates. Its dephasing efficiency becomes independent of first-order quadrupolar effects yet shows a high sensitivity to second-order offsets. A constant-time/variable-offset recoupling sequence thus provides a simple route to acquire, in an indirect fashion, (14)N overtone spectra from rotating powders. The principles underlying this kind of S-(14)N experiments and different applications involving S = (13)C, (59)Co sites are presented.     

Behavior of peptides and computer-assisted optimization of peptides separations in a normal-phase thin-layer chromatography system with and without the addition of ionic liquid in the eluent

The addition of an ionic liquid into the mobile phase appeared to be useful in optimization of chromatographic separation of peptides. Different behavior of peptides in thin-layer chromatography (TLC) was observed after addition of 1-ethyl-3-methylimidazolium tetra fluoroborate to the eluent in comparison to the system without the ionic liquid. Nonlinear dependence of the retention coefficient, R(M), of peptides on the volume percentage of acetonitrile in the eluent was found in normal-phase TLC with and without immidazolium tetra fluoroborate in the mobile phase. In general, R(M) increased with increasing concentration of acetonitrile. In TLC systems without the ionic liquid, R(M) can be described well with a quadratic function. On the other hand, in a TLC system with an ionic liquid as the additive to the mobile phase, the retention behavior is better described with a third-degree polynomial function. The potential usefulness of ionic liquids for optimization of separation of peptides was demonstrated. Optimization of the separation conditions was supported by a commercially available computer program.     

Calculation of kinetic parameters from TG curve on the base of dehydration process of hydrous titanium dioxide

A direct method of evaluating of kinetic equation parameters based on TG curve is proposed. The method was applied to calculate kinetic parameters of the process of dehydration of hydrous titanium dioxide.

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Zusammenfassung Es wird ein direktes Verfahren zur Bestimmung der Parameter der kinetischen Gleichung auf der Basis von TG-Kurven gegeben. Das Verfahren wurde zur Berechnung der kinetischen Parameter des Dehydratationsprozesses von wasserhaltigem Titandioxid benutzt.

     

Applications of uniform asymptotic regularity to fixed point theorems

In this paper, we show that there are no nontrivial surjective uniformly asymptotically regular mappings acting on a metric space, and we derive some consequences of this fact. In particular, we prove that a jointly continuous left amenable or left reversible semigroup generated by firmly nonexpansive mappings on a bounded \({\tau}\)-compact subset of a Banach space has a common fixed point, and we give a qualitative complement to the Markov–Kakutani theorem.