Effect of Mechanical Activation on the Reactivity of Reagents in the Preparation of Lithium Ferrites

Russian Physics Journal -     

Synthesis of Polyol Tetrabromophthalate and Its Use as a Component for Preparing Foamed Polyurethanes of Reduced Flammability

A procedure was suggested for preparing brominated polyols of reduced viscosity for the synthesis of foamed polyurethanes of reduced flammability. The flame-retarding action of the synthesized polyol tetrabromophthalate in polyurethane was studied in comparison with that of other widely used flame retardants. Evaluation of the effect exerted on the flammability of the polurethane compound by the polyol tetrabromophthalate synthesized, melamine, and aluminum hydroxide shows that all the samples containing flame retardants are self-extinguishing. The shortest combustion time was observed for the sample containing 6% polyol tetrabromophthalate synthesized. The sample containing as a flame retardant additive solely the synthesized polyole tetrabromophthalate also exhibits the highest performance as a heat-insulating material from the viewpoint of thermal conductivity.

     

The Effect of Atmospheric Ionization on Oxygen Diffusion in Polycrystalline Ferrites under e-Beam Irradiation

It is shown that activation of the process of oxygen diffusion in polycrystalline lithium-titanium ferrites heated by a beam of high-energy electrons in the range of temperatures 873–1173 K occurs due to two factors: gas medium ionization by an e-beam and acceleration of diffusion processes directly in the matrix in the irradiation field.     

Radiative decays of ρ and ω mesons

The results of the measurements of radiative decays of ρ and ω mesons with the Neutral Detector at thee ⁺ e ^? collider VEPP-2M are presented. The branching ratio of the decay ω→π ⁰γ was measured with higher than in previous experiments accuracy: $${\rm B}(\omega \to \pi ^0 \gamma ) = 0.0888 \pm 0.0062$$ . The ρ⁰→π ⁰ γ branching ratio was measured for the first time: $$B(\rho ^0 \to \pi ^0 \gamma ) = (7.9 \pm 2.0) \cdot 10^{ - 4} $$ . The decays ρ, ω→ηγ were studied. Their branching ratios with the assumption of constructive ρ?ω interference are: $$\begin{gathered} B(\omega \to \eta \gamma ) = (7.3 \pm 2.9) \cdot 10^{ - 4} , \hfill \\ B(\rho \to \eta \gamma ) = (4.0 \pm 1.1) \cdot 10^{ - 4} \hfill \\ \end{gathered} $$ . The branching ratios of ρ, ω→ηγ and ω→e ⁺ e ^? decays were also measured: $$\begin{gathered} B(\omega \to \pi ^ + \pi ^ - \pi ^0 ) = 0.8942 \pm 0.0062, \hfill \\ B(\omega \to e^ + e^ - ) = (7.14 \pm 0.36) \cdot 10^{ - 5} \hfill \\ \end{gathered} $$ . The upper limit for the ω→π ⁰ π ⁰ γ branching ratio was placed: B(ω→π ⁰ π ⁰ γ)<4·10^?4 at 90% confidence level.     

Synthesis of 2-amino-5-cyano-1,3,4-oxadiazole and some of its derivatives

Preparative syntheses have been developed for 2-amino-5-cyano-1,3,4-oxadiazole from the semicarbazone of methyl glyoxylate and some of its transformations were studied. This product is an important intermediate in the preparation of its derivatives.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1. 243–246, January, 1991.     

Mechanism of the oxidative carbonylation of terminal alkynes at the ≡C-H bond in solutions of palladium complexes

The formation mechanism of the active catalyst in the oxidative carbonylation of terminal alkynes at the ≡C-H bond has been investigated for the catalytic system Pd(OAc)₂-PPh₃-p-benzoquinone (Q)-MeOH. It has been demonstrated by NMR spectroscopy, X-ray crystallography, and kinetic measurements that the catalytically active palladium is in the oxidation state 0 and is bound into complexes stabilized by p-benzoquinone (PdL₂Q, where L = PPh₃). A mechanism is suggested for the catalytic process, which includes the formation of the complex PdL₂Q, the oxidative addition of the alkyne to this complex at the ≡C-H bond, the insertion of CO into the Pd-C bond, and steps in which hydride hydrogen is intramolecularly transferred to the p-quinone.     

Mechanism of the cyclization of dimethyl diethynyl silane with selenium tetrabromide: Computational and structural studies, and monitoring

The structure of 2,4-dibromo-2-dibromomethyl-3,3-dimethyl-1-selena-3-silacyclopentene-4, formed by regioselective electrophilic addition of SeBr₄ to dimethyl diethynyl silane, has been determined using X-ray analysis technique. Quantum chemistry methods were used to study elementary stages of the reaction. It was found that the first stage consisted of SeBr₄ conversion into bimolecular complex Br₂?SeBr₂, initiated by dimethyl diethynyl silane. Possible formation of five-membered and six-membered heterocycles involves different cyclization mechanisms. The formation of only five-membered heterocycle is explained by kinetically preferable ring closure through four-center transition state. The conclusions obtained by calculations were confirmed by monitoring of the reaction using ¹H NMR method.     

Sorption–Desorption Photometric Determination of Trace Iron in Sodium, Potassium, and Ammonium Thiocyanates Using Polyurethane Foams

A reagent-free sorption photometric method for determining trace iron(III) in alkali-metal and ammonium thiocyanates was developed. The method consists in the adsorption of iron(III) thiocyanate complexes on polyurethane foams at pH 2–3 followed by the desorption of complexes with acetone and a measurement of the absorbance of solutions. The analytical range for iron was 0.5–20 g in a 0.2–2.5-g portion of salt. The determination limit and relative standard deviation were 2 × 10^–5% and 20–30%, respectively (n= 3; P= 0.95). The specific feature of the determination is that an additional photometric reagent is not introduced in the solution of the salt to be analyzed, because thiocyanate, that is, the matrix component of the test sample, acts as such a reagent.     

Diverse redox-active molecules bearing O-, S-, or Se-terminated tethers for attachment to silicon in studies of molecular information storage

A molecular approach to information storage employs redox-active molecules tethered to an electroactive surface. Attachment of the molecules to electroactive surfaces requires control over the nature of the tether (linker and surface attachment group). We have synthesized a collection of redox-active molecules bearing different linkers and surface anchor groups in free or protected form (hydroxy, mercapto, S-acetylthio, and Se-acetylseleno) for attachment to surfaces such as silicon, germanium, and gold. The molecules exhibit a number of cationic oxidation states, including one (ferrocene), two [zinc(II)porphyrin], three [cobalt(II)porphyrin], or four (lanthanide triple-decker sandwich compound). Electrochemical studies of monolayers of a variety of the redox-active molecules attached to Si(100) electrodes indicate that molecules exhibit a regular mode of attachment (via a Si-X bond, X = O, S, or Se), relatively homogeneous surface organization, and robust reversible electrochemical behavior. The acetyl protecting group undergoes cleavage during the surface deposition process, enabling attachment to silicon via thio or seleno groups without handling free thiols or selenols.     

Experimental study of the evolution of perturbations in the supersonic wake behind a flat plate

The evolution of perturbations in the wake of a flat plate (with symmetric wedge-shaped nose and tail) is studied experimentally at the Mach number M=2 for various plate thicknesses and tail lengths.Novosibirsk. Translated from Izvestiya Rossiiskoi Akademii Nauk, Mekhanika Zhidkosti i Gaza, No. 4, pp. 167–171, July–August, 1996.