Electrochemical reduction of sodium metavanadate in an equimolar KCl-NaCl melt

Electrochemical reduction of sodium metavanadate in an equimolar KCl-NaCl melt and the effect of acid-base properties of environment on this process are studied by a voltammetry method on a stationary platinum electrode. It is established that the limiting current of the NaVO₃ electroreduction process has a kinetic nature. The process proceeds via an autoinhibition scheme and its rate is limited by an acid-base reaction conjugated with an irreversible charge transfer reaction. A substantial role of cationic composition of the melt is revealed experimentally. Following acidification of the KCl-NaCl-NaVO₃ melt by Mg²⁺ (from MgCl₂), the process passes from an irreversible kinetic regime into a reversible diffusion (quasi-diffusion) process. Values of stability constants for vanadates produced with the aid of acid-base titration of vanadium pentoxide by oxygen ions in experimental conditions are presented. These values are taken into account when calculating kinetic parameters of the NaVO₃ electroreduction.     

Sulfurization polyvinyl chloride

A sulfurized polymer comprising 57.64% of chemically bound sulfur characterizing by paramagnetism with the concentration of paramagnetic centers 2 × 10¹⁹ spins g^?1 and g-factor 2.0043 was resulted n the treatment of industrial polyvinyl chloride by elemental sulfur.     

Humic-based bionanocomposites containing stable paramagnetic gold nanoparticles for prospective use in pharmaceuticals

Structural peculiarities and supramolecular organization of medicinally promising nanocomposites, synthesized from humic substances, which essentially differ depending on decomposition degree, have been studied using electron spin resonance, transmission electron, and confocal laser scanning microscopy techniques and some other modern physical–chemical methods. It is shown that stable zero-valent gold nanoparticle of about 10–17?nm in size are formed in a natural macromolecular matrix. The nanocomposites obtained turn out to be stable in aggregative state for a long time and preserve their properties that are extremely important for prospective medicinal substances.     

New photochemical transformations of 1-iodopropan-2-one

Photolysis of 1-iodopropan-2-one (λ = 254 nm) at 80–90°C in the absence of CCl₄ was studied. The structure of obtained polymer was studied by ¹H NMR, IR, and ESR spectroscopy.     

Superradiance by a system of highly polarized exchange-coupled nonequivalent spins

We propose a model of radiofrequency (rf) superradiance by a system of interacting nonequivalent spins in a point specimen. In contrast to the rf superradiance observed and described earlier, here spin-spin coupling acts as the interaction with the cavity. To be definite, we examine the spins of two isotopes of a metal that are coupled by the Ruderman-Kittel interaction. The analysis of such a system when the magnetization of one spin species is inverted shows that the system can have one resonance frequency and two different decay times, instead of two resonance frequencies and one decay time in the usual situation. When such “repulsion” of decay times occurs and the absolute values of the spin polarizations are large, transverse magnetization increases and exhibits features characteristic of superradiance. Finally, we calculate the parameters of this superradiance: the voltage across the terminals of an rf pickup coil, the pulse length, the delay time, and the superradiant intensity. Zh. éksp. Teor. Fiz. 112, 551–563 (August 1997)     

Fe-containing nanocomposites based on a biocompatible copolymer 1-vinyl-1,2,4-triazole with <Emphasis Type="Italic">N</Emphasis>-vinylpyrrolidone

New polymer nanocomposites containing iron oxide nanoparticles stabilized with a biocompatible copolymer of 1-vinyl-1,2,4-triazole with N-vinylpyrrolidone were produced. The synthesis was conducted using the method of chemical reduction of iron ions with hydrazine hydrate in an aqueous medium in the presence of a polymer matrix. The ESR spectroscopy data showed that the core—shell type nanoparticles were obtained. The core generally consistsed of zero-valence iron coated with an oxide shell. According to the data of transmission electron microscopy, the obtained polymer nanocomposites consisted of nanoparticles of mainly spherical shape with a diameter from 1 to 14 nm. Aggregates formed from individual stabilized nanoparticles of up to 75 nm in size (in most cases) were also observed. These aggregated particles were found to self-organize and form branched chains. Nanocomposites were characterized by a different particle-size distribution, which was determined by the initial ratio of the copolymer and the precursor of iron nanoparticles.     

ESR and longitudinal response in metals containing localized paramagnetic centers with spin<Emphasis Type="Italic">S</Emphasis>>1/2

The theory describing electron spin resonance (ESR) and the longitudinal magnetization response of coupled spin systems in a metal containing both delocalized conduction electrons (“espins”) and localized paramagnetic centers (“s-spins”) is generalized to the case of arbitrary half-integer spin value,S>1/2, of the s-spins. The consideration is based on the Bloch-Hasegawa equations supplemented by taking into account the coupled evolution of the longitudinal magnetization components and the effect of weak ESR saturation by the microwave field. The ESR transversal susceptibility and longitudinal magnetization response are worked out in terms of normal modes related to the coupled s- and e-spin oscillators taking into account the ESR fine structure (FS) of the s-spins. These modes are characterized by effective (renormalized) frequencies and relaxation rates (decays) which differ from the partial ones. In the specific cases of a well-resolved FS (in the isothermal limit) and of the relaxational collapse of the FS due to strong exchange coupling between the s- and e-spins (in both the isothermal and bottlenecked limits), the analytical expressions are derived which are relevant to the modulation technique of measuring extremely fast spin-lattice relaxation times in metals.     

Stereochemical study of iminodihydrofurans based on experimental measurements and SOPPA calculations of (13)C-(13)C spin-spin coupling constants

Configurational assignment and conformational analysis of a series of iminodihydrofurans obtained from cyanoacetylenic alcohols were performed on the basis of experimental measurements and high-level ab initio calculations of their (13)C-(13)C spin-spin coupling constants. The title compounds were shown to form and exist in solution as the individual Z isomers, adopting the orthogonal orientation of the amino, alkylamino and dialkylamino groups and the s-trans orientation of the CONH(2) group at the C(4) position of the 2,5-dihydro-2-iminofuran moiety.     

Isolation and properties of a thermostable endoglucanase from a thermophilic mutant strain ofTielavia terrestris

A heat-stable enzyme was isolated from the cellulase complex of a thermophilic strain of the micromyceteThielavia terrestris. The purified enzyme exhibited both endoglucanase and xylanase activities and had a mol mass of 69,000 Daltons and an isoelectric point of 6.4. When the cells were grown at 48°C, the initial activity of the purified enzyme using carboxymethylcellulose as a substrate was 150 nkat/mg and the Michaelis constant was 6.6 g/L. The heat stability of the enzyme was high, losing only 20% of the initial activity after a 6-h incubation at 65 °C. When cultures were grown on microcrystalline cellulose and xylose was added after 48 h of growth, endoglucanase and xylanase activities were more than doubled. Similar increases in these activities were observed by growing the cultures on straw.     

NMR spectra under skin-effect conditions at ultralow temperatures

An investigation based on the coupled Maxwell-Bloch equations for a system of equivalent exchange-coupled spins is performed in order to explain a number of features of NMR spectra obtained in metals by Fourier-transforming of the free-induction decay at ultralow temperatures. Small angles of tilting of the nuclear magnetization by the exciting rf field are considered. It is shown that the free precession inherits the nonuniformity in the distribution of the rf field and the magnetization produced at the excitation stage inside the sample on account of the skin effect. As a result, the NMR spectrum is found to consist of a set of peaks—signals due to standing spin waves. However, such a spectrum can be observed only when the detuning of the exciting rf field is sufficiently large relative to the Larmor frequency of the spins. Otherwise, the rf field does not penetrate into the sample because of strong absorption by the spins. If the detuning is large, the dispersion signal and part of the NMR absorption signal are proportional to the equilibrium magnetization to the power 3/2. Such behavior is expected at low temperatures so that the coupling of the magnetization with the rf field is strong. The results obtained qualitatively explain the experimentally observed characteristics of the NMR spectra: the presence of kinks and structure of the NMR lines, the dependence of the shape and intensity of the spectrum on the detuning of the exciting rf field, and the nonlinear dependence of the nuclear susceptibility on the reciprocal of the sample temperature. Zh. éksp. Teor. Fiz. 114, 1836–1847 (November 1998)