Deactivation reactions in the modeled 2,2,6,6‐tetramethyl‐1‐piperidinyloxy‐mediated free‐radical polymerization of styrene: A comparative study with the 2,2,6,6‐tetramethyl‐1‐piperidinyloxy/acrylonitrile system

The competitiveness of the combination and disproportionation reactions between a 1‐phenylpropyl radical, standing for a growing polystyryl macroradical, and a 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO) radical in the nitroxide‐mediated free‐radical polymerization of styrene was quantitatively evaluated by the study of the transition geometry and the potential energy profiles for the competing reactions with the use of quantum‐mechanical calculations at the density functional theory (DFT) UB3‐LYP/6‐311+G(3df, 2p)//(unrestricted) Austin Model 1 level of theory. The search for transition geometries resulted in six and two transition structures for the radical combination and disproportionation reactions, respectively. The former transition structures, mainly differing in the out‐of‐plane angle of the N? O bond in the transition structure TEMPO molecule, were correlated with the activation energy, which was determined to be in the range of 8.4–19.4 kcal mol^?1 from a single‐point calculation at the DFT UB3‐LYP/6‐311+G(3df, 2p)//unrestricted Austin Model 1 level. The calculated activation energy for the disproportionation reaction was less favorable by a value of more than 30 kcal mol^?1 in comparison with that for the combination reaction. The approximate barrier difference for the TEMPO addition and disproportionation reaction was slightly smaller for the styrene polymerization system than for the acrylonitrile polymerization system, thus indicating that a β‐proton abstraction through a TEMPO radical from the polymer backbone could diminish control over the radical polymerization of styrene with the nitroxide even more than in the latter system. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 232–241, 2007     

Determination of Emodin and Phenolic Acids in the Petioles of Rheum undulatum and Rheum rhaponticum

JPC – Journal of Planar Chromatography – Modern TLC - Emodin and twelve phenolic acids (ellagic, gallic, protocatechuic, homoprotocatechuic, caffeic, p-hydroxybenzoic, p-coumaric,...     

On invariability of self-injective algebras of tilted type under stable equivalences

We prove that a large class of self-injective algebras of tilted type is invariant under stable equivalences of module categories.

     

Searching for new conditions for fermion N-representability

New elements of the dual cone of the set of fermion N-representable 2-density operators are proposed. So far, the explicit form of the corresponding necessary conditions for N-representability is obtained for N = 3. In this case the new condition is stronger than the known B- and C-conditions for 3-representability. The results provide evidence that in the spectral decomposition of the N-representable 2-density operator there exists an intrinsic relation between the eigenvalue and the corresponding eigenfunction.     

Thermal Analysis in Examination of Reduction of Blast Furnace Pellets

This paper presents applications of thermal analysis to observe the course of reduction of acidic pellets, metallurgical substances whose reducibility and strength are basic parameters of use in blast furnace processes. Both parameters depend on the mineral composition of the samples. The investigations included determination of the chemical and phase compositions of the initial samples and reduction products. Research was conducted on acidic pellets from Połtawa (Poland), applied in the T. Sendzimir Steelworks (Poland), in comparison with pellets from Brazil, Canada and Lebedyn (Russia). This revised version was published online in August 2006 with corrections to the Cover Date.     

On mechano-chemical Calcium waves

The influence of mechano-chemical coupling on calcium concentration waves is considered. The propagation of calcium waves is described by a reaction–diffusion equation with the reaction term dependent on the mechanical stress responsible for the release of calcium. Similarly the balance of mechanical forces is influenced by the calcium concentration through the so-called traction force.     

Hausdorff Measures versus Equilibrium States of Conformal Infinite Iterated Function Systems

Dealing with infinite iterated function systems we introduce and develop the ergodic theory of Hölder systems of functions similarly as in [HU] and [HMU]. In the context of conformal infinite iterated function systems we prove the volume lemma for the Hausdorff dimension of the projection onto the limit set of a shift invariant measure. This can be considered as a Billingsley type result. Our cenral goal is to demonstrate the appearance of the "singularity-absolute continuity" dichotomy for equilibrium states of Hölder systems of functions which has been observed in [PUZ,I] and [PUZ,II] (see also [DU1] and [DU2]) in the setting of rational functions of the Riemann sphere.     

Properties of Ergodic Projection for Quantum Dynamical Semigroups

We study properties of ergodic projection forquantum dynamical semigroups on W *-algebras. Inparticular, we describe the normal and singular parts ofthis projection, characterize normal invariantfunctionals, and derive some conclusions for ergodicsemigroups.