Graft polymerization of vinyl monomers inside macroporous polyacrylamide gel,cryogel, in aqueous and aqueous‐organic media initiated by diperiodatocuprate(III) complexes

Graft polymerization initiated by diperiodatocuprate(III) complex (Cu(III)) initiator was found to be an effective and convenient method for graft polymerization of vinyl monomers onto macroporous polyacrylamide gels, the so‐called cryogels (pAAm‐cryogels). The effect of time, temperature, monomer and initiator concentration during the graft polymerization in aqueous and aqueous‐organic media was studied. The graft polymerization of water‐soluble monomers as [2‐(methacryloyloxy)ethyl]‐trimethylammonium chloride, 2‐hydroxyethyl methacrylate, N‐isopropylacrylamide, and N,N‐dimethylacrylamide proceeds with higher grafting yield in aqueous medium, as compared with that in aqueous‐organic media. Graft polymerization in aqueous‐organic media such as water–DMSO solutions allows grafting of water‐insoluble monomers such as glycidyl methacrylate and N‐tert‐butylacrylamide with high grafting degrees of 100 and 410%, respectively. It was found that the deposition of initiator on the pore surface of cryogels promoted graft polymerization by facilitating the formation of the redox couple Cu(III)‐acrylamide group. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1952–1963, 2006     

Variation of geometric invariant theory quotients

Geometric Invariant Theory gives a method for constructing quotients for group actions on algebraic varieties which in many cases appear as moduli spaces parameterizing isomorphism classes of geometric objects (vector bundles, polarized varieties, etc.). The quotient depends on a choice of an ample linearized line bundle. Two choices are equivalent if they give rise to identical quotients. A priori, there are infinitely many choices since there are infinitely many isomorphism classes of linearized ample line bundles. Hence several natural questions arise. Is the set of equivalence classes, and hence the set of non-isomorphic quotients, finite? How does the quotient vary under change of the equivalence class? In this paper we give partial answers to these questions in the case of actions of reductive algebraic groups on nonsingular projective algebraic varieties. We shall show that among ample line bundles which give projective geometric quotients there are only finitely many equivalence classes. These classes span certain convex subsets (chambers) in a certain convex cone in Euclidean space, and when we cross a wall separating one chamber from another, the corresponding quotient undergoes a birational transformation which is similar to a Mori flip.     

Non-steady state homogeneous nucleation in glass-forming systems: Dimensionless kinetic equation

The kinetic equation of the classical homogeneous nucleation theory is rewritten in dimensionless form and it is shown that the numerical computation of the dimensionless kinetic equation is approximately 20 times faster in comparison with the original kinetic equation. The results are compared with known analytical results and with previous numerical results in the case of the constant and variable temperature for the model Li₂O.2 SiO₂ melt. It is shown, e.g., that under non-isothermal conditions the nucleation rate is greater than the quasistationary nucleation rate and the cluster distribution function is greater than the corresponding quasiequilibrium cluster distribution function.     

On the bootstrap effect in large tokamaks with lower hybrid driven current

The amplification of lower hybrid (LH) driven current of various profiles has been found. The results strongly depend on the plasma temperature profile, on the LH current profile, and on the magnitude of the particle diffusion flux.This work was started during the visit of the author in the I. V. Kurchatov Institute of Atomic Energy, Moscow. The author thanks IAE for hospitality, and V. Parail, G. V. Pereverzev, A. Smoljakov and R. Klíma for many useful and critical discussions.     

Quantitative characterization of chaotic instabilities in semiconductors

A method for quantitative characterization of chaotic dynamical systems is discussed. An electronic instrument for determining the number of independent variablesk ^*, involved in the motion, is described. It allows one to obtain these in real time from a single observable. The suggested technique has been applied to quantification of strange attractors underlying chaotic instabilities in semi-insulating GaAsCr, and n-Ge, irradiated with high energy electrons. In n-Ge, for instance, the measured numbersk ^* range from 2 to 4 depending on control parameters. These measurements reveal the highly deterministic nature of the observed chaotic oscillations. The physical mechanisms responsible for the current instabilities and chaotic behaviour are discussed.     

Thermal coefficient of linear expansion of non-crystalline chalcogenides in the As-S-Se-Te-I system

The object of the paper is an investigation of the glasses of the (As₂S₃)_x(AsSe_0.5Te_0.5I)_100-x. type for 65≤;x≤;95, using methods of thermomechanical analysis. Values of the thermal coefficients of linear expansion in solid and visco-plastic phase were determined. it was shown that introducing arsenic-sulfide in glass-matrix AsChI, i.e. (AsSe_0.5Te_0.5I), leads to an increasing stability of these glasses. The characteristic temperatures of softening Tg and the temperature of the beginning of deformation t_w increase by increasing content of As₂S₃. The analytical forms of dependence of four significant physical values α_g, α_l, Tg, Tw, as a function of As₂S₃ content in the structure of glasses were fitted. This revised version was published online in July 2006 with corrections to the Cover Date.     

Nitroxides with two pK values--useful spin probes for pH monitoring within a broad range

A series of 4-dialkylamino-2,5-dihydroimidazole nitroxides with pyridine-4-yl, 4-dimethylaminophenyl or 4-hydroxyphenyl groups in position 2 of the imidazole ring were prepared using the reaction of RMgBr with corresponding 5-dialkylamino-4,4-dimethyl-4H-imidazole 3-oxides. The EPR spectra of the nitroxides were shown to be pH-sensitive due to consecutive protonation of the amidino moiety and the basic group(s) at position 2 of the imidazole ring. The 5,5-dimethyl-4-(dimethylamino)-2-ethyl-2-pyridine-4-yl-2,5-dihydro-1H-imidazol-1-oxyl showed a monotonic increase in the isotropic nitrogen hyperfine (hfi) coupling constant alpha(N) of 1 .4 G over a pH range from 2 to 6.5. Such a broad range of pH-sensitivity could be useful for many biophysical and biomedical applications, including pH-monitoring in the stomach.     

Zur Kenntnis von Natrium-hexafluoromanganat(III)

Sodium hexafluoromanganate(III) has been synthesized by heating equimolecular quantities of Na₂MnF₅ and NaF in argon atmosphere. The compound is monoclinic witha=5.56 (1) Å,b=5.84 (1) Å,c=8.10 (2) Å, =90.7 (2) andZ=2. It is a high spin complex with _eff and the deformation of the octahedra is evident from its IR-spectra. Two enantiotropic transitions (at 562 and 653°C) and the melting point at 800°C have been observed.

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8. Mitt.: Mh. Chem.106, 483 (1975).     

Electrocatalysis by foreign metal monolayers: Oxidation of formic acid on platinum

It was demonstrated that some foreign metal monolayers formed by underpotential deposition have pronounced catalytic effects on the oxidation of formic acid on platinum. The explanation of these effects was sought within the framewor of existing data on the formic acid oxidation and the underpotential deposition. It was found that the catalytic effect of foreign metal monolayers originates in the decrease of hydrogen adsorption thus preventing the formation of the main poisoning species COH. At the same time these experiments confirm the previously postulated mechanism of formation of the poisoning species involving adsorbed hydrogen.