Plasmochemical Neutralization of Ozone-Destroying Chladones and Fluorine- and Chlorine-containing Wastes

A plasmochemical technique for neutralizing ozone-destroying chladones and fluorine- and chlorine-containing wastes is considered. Experimental results obtained on applying this technique to neutralization of some halogen-containing substances are presented, together with the information gained on using the technological scheme of the process in designing and constructing an industrial installation for neutralizing wastes of a plant manufacturing polytetrafluoroethylene.     

Thermoresponsive behavior of water-salt solutions of a graft copolymer with a main polyimide chain and side poly(<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-dimethylamino-2-ethyl methacrylate) side chains

The water-salt solutions of the graft copolymer bearing a polyimide main chain and poly(N,N-dimethylamino-2-ethyl methacrylate) side chains (M = 4.7 × 10⁵, the density of grafting with side chains z = 0.44) are studied by static and dynamic light scattering and turbidimetry. The solutions are investigated in a tenfold range of NaCl concentrations (from 0.015 to 0.15 mol/L) at the polymer concentration from 0.002 to 0.015 g/cm³ and pH from 8 to 12. The temperature dependences of the intensity of scattered light, optical transmission, hydrodynamic radius of scattering objects, and their concentrations in solutions are derived. The temperatures of phase separation onset T ₁ and end T ₂ are determined. It is shown that an increase in the salt content in solution leads to reduction in the polymer solubility and in temperatures T ₁ and T ₂. The watersalt solutions retain all the regularities of phase-separation temperature variation observed for aqueous solutions with change in the concentration of solution and pH of a medium: the values of T ₁ and T ₂ increase upon dilution and growth of acidity.     

A Jeffrey-fluid model of blood flow in tubes with stenosis

In this paper, we discuss the two-layered Jeffrey-fluid model with mild stenosis in narrow tubes. The blood flow in narrow arteries is treated as a two-fluid model with the suspension of erythrocytes, leukocytes, etc., as a Jeffrey fluid, which is a non-Newtonian fluid, in the core region and plasma, a Newtonian fluid, in the peripheral region. An analytical solution has been obtained for the velocity in the core and peripheral region, volume flow rate, resistance to flow, and wall-shear stress. The effect of Jeffrey-fluid parameters, like the height of stenosis, viscosity, etc., on volume flow rate, resistance to flow (impedance), and wall-shear stress has been discussed graphically. Through the present study, it is found that the wall-shear stress and resistance to flow increases with the increase in height of stenosis and decreases with the increase in the ratio of relaxation time. It is also found that the velocity decreases with an increase in stenosis height in both the core and the peripheral region. A previous result has been also verified.     

Photophysics and photochemistry of uranyl ions in aqueous solutions: Refining of quantitative characteristics

The photochemistry and photophysics of aqueous solutions of uranyl nitrate have been investigated by nanosecond laser photolysis with excitation at 266 and 355 nm and by time-resolved fluorescence spectroscopy. The quantum yield has been determined for (UO₂²⁺)* formation under excitation with λ = 266 and 355 nm light (φ = 0.35). The quantum yield of uranyl luminescence under the same conditions is 1 × 10^–2 and 1.2 × 10^–3, respectively, while the quantum yield of luminescence in the solid state is unity, irrespective of the excitation wavelength. The decay of (UO₂²⁺)* in the presence of ethanol is biexponential. The rate constants of this process at pH 3.4 are k₁ = (2.7 ± 0.2) × 10⁷ L mol^–1 s^–1 and k₂ = (5.4 ± 0.2) × 10⁶ L mol^–1 s^–1. This biexponential behavior is explained by the existence of different complex uranyl ion species in the solution. The addition of colloidal TiO₂ to the solution exerts no effect on the quantum yield of (UO₂²⁺)* formation or on the rate of the reaction between (UO₂²⁺)* and ethanol. The results of this study have been compared with data available from the literature.     

Multicenter polyester initiators for the synthesis of graft copolymers with oligo(2-ethyl-2-oxazoline) side chains

Multicenter alkylene-aromatic polyester initiators for the cationic polymerization of oxazolines are synthesized via the high-temperature polycondensation of 2-[4-(2-Br-ethyl)]phenylsulfonyl hydroquinone with 4,4'- (alkanoyldioxydibenzoyl)dichlorides. The Kuhn segment values, liquid-crystalline properties, and molecularmass characteristics of the macroinitiators are determined. It is shown that the obtained polyesters may be used as initiators for the cationic polymerization of 2-ethyl-2-oxazoline. The graft copolymers form aqueous micellar solutions with a narrow particle-size distribution and possess a lower critical solution temperature.     

Using conformationally locked nucleosides to calibrate the anomeric effect: Implications for glycosyl bond stability

Steric and electronic parameters, such as the anomeric effect (AE) and gauche effect play significant roles in steering the North&lrarr;South equilibrium of nucleosides in solution.Two isomeric oxa-bicyclo[3.1.0]hexane nucleosides that are conformationally locked in either the North or the South conformation of the pseudorotational cycle were designed to study the consequences of having the AE operational or not, independent of other parameters. The rigidity of the system allowed the orientation of the orbitals involved to be set in ‘fixed’ relationships, either antiperiplanar where the AE is permanently ‘on’, or gauche where the AE is impaired. The consequences of these two alternatives were subjected to high-level calculations and measured experimentally by X-ray crystallography, hydrolytic stability of the glycosyl bond, and pK_a values.     

Molecular and hydrodynamic characteristics of star-shaped polystyrenes with one or two fullerene (C<Subscript>60</Subscript>) molecules as a branching center

The molecular properties of regular star-shaped polystyrenes with different numbers of arms (6, 12, and 22) and different structures of the branching center (one or two covalently bonded fullerene C60 molecules) are studied by static light scattering; translational diffusion; and viscometry in toluene, THF, and chloroform. The lengths of the arms for the studied polymer stars are found to be the same. (The molecular mass of the arm is 8.1 × 10³.) The molecular mass and hydrodynamic sizes of macromolecules are estimated. It is shown that the conformational and hydrodynamic characteristics of polymer stars remain practically unchanged on passage from THF to chloroform. Compared to the linear analog, star-shaped fullerene-containing PSs are characterized by a higher density of the molecular coil. The shape of their macromolecules differs insignificantly from spherical, in consistence with theoretical predictions for polymer stars with relatively short arms.     

Molecular properties of conjugates formed by synthetic hydrophilic polymers and sterically hindered phenols

Water-soluble conjugates are prepared via the chemical modification of poly(vinyl alcohol) and poly(ethylene glycol) by antioxidants taken from the family of sterically hindered phenols. The effects of the degree of substitution of conjugates on the dimensions of molecules and their aggregates are studied by viscometry and light scattering in dilute solutions. It is shown that an increase in the amount of antioxidant groups incorporated into the poly(vinyl alcohol) chain leads to a decrease in the dimensions of single conjugate molecules owing to attraction of hydrophobic groups. Poly(ethylene glycol) molecules carrying end groups of sterically hindered phenols form micellar aggregates that are absent in the solution of the initial polymer. The mean number of molecules involved in such an aggregate is 83. It is found that the presence of hydrophobic end groups in poly(ethylene glycol) molecules causes a sharp reduction in the lower critical solution temperature of a solution relative to that of the initial polymer.     

Dimerization mechanism of bis(triphenylphosphine)copper(I) tetrahydroborate: proton transfer via a dihydrogen bond

The mechanism of transition-metal tetrahydroborate dimerization was established for the first time on the example of (Ph(3)P)(2)Cu(η(2)-BH(4)) interaction with different proton donors [MeOH, CH(2)FCH(2)OH, CF(3)CH(2)OH, (CF(3))(2)CHOH, (CF(3))(3)CHOH, p-NO(2)C(6)H(4)OH, p-NO(2)C(6)H(4)N═NC(6)H(4)OH, p-NO(2)C(6)H(4)NH(2)] using the combination of experimental (IR, 190-300 K) and quantum-chemical (DFT/M06) methods. The formation of dihydrogen-bonded complexes as the first reaction step was established experimentally. Their structural, electronic, energetic, and spectroscopic features were thoroughly analyzed by means of quantum-chemical calculations. Bifurcate complexes involving both bridging and terminal hydride hydrogen atoms become thermodynamically preferred for strong proton donors. Their formation was found to be a prerequisite for the subsequent proton transfer and dimerization to occur. Reaction kinetics was studied at variable temperature, showing that proton transfer is the rate-determining step. This result is in agreement with the computed potential energy profile of (Ph(3)P)(2)Cu(η(2)-BH(4)) dimerization, yielding [{(Ph(3)P)(2)Cu}(2)(μ,η(4)-BH(4))](+).     

The behavior of thermoresponsive star-shaped poly-2-isopropyl-2-oxazoline in saline media

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