Degradative chain transfer in vinyl acetate polymerizations using toluene as solvent

In this work, we propose that retardation in vinyl acetate polymerization rate in the presence of toluene is due to degradative chain transfer. The transfer constant to toluene (C_trs) determined using the Mayo method is equal to 3.8 × 10^?3, which is remarkably similar to the value calculated from the rate data, assuming degradative chain transfer (2.7 × 10^?3). Simulations, including chain‐length‐dependent termination, were carried out to compare our degradative chain transfer model with experimental results. The conversion–time profiles showed excellent agreement between experiment and simulation. Good agreement was found for the M_n data as a function of conversion. The experimental and simulation data strongly support the postulate that degradative chain transfer is the dominant kinetic mechanism. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3620–3625, 2007     

Application of N,N‐bis(diphenylphosphino)aniline palladium(II) complexes as pre‐catalysts in Heck coupling reactions

Palladium(II) complexes with N,N‐bis(diphenylphosphino)aniline ligands catalyse the Heck reaction between styrene and aryl bromides, affording stilbenes in good yield. The structures of two of the complexes used as pre‐catalysts have been determined by single‐crystal X‐ray diffraction. Copyright © 2007 John Wiley & Sons, Ltd.     

Structure of norbornene-fused 3,1-oxazine double cycloadducts

Pentacyclic isoxazolines were obtained by the cycloaddition of benzonitrile oxide to norbornene-azetidinone-fused 3,1-oxazines. The constitutions of two of the isomers obtained, and the configurations and conformations of all products, were determined by means of ¹H and ¹³C NMR spectroscopy and DNOE experiments.     

Phasing of three vircators simulated in terms of coupled van der Pol oscillators

Phase synchronization in a system of three virtual-cathode microwave oscillators (vircators) simulated by coupled van der Pol oscillators is studied. The phasing dynamics of the vircators is visualized with the phase portraits of the system in the triangular coordinates. Different phasing conditions are found.     

Fundamental aspects of initiated oxidation of tridecane and polyethylene in solutions

Specific features of the initiated oxidation of polyethylene and its low-molecular-weight analogue tridecane, associated with the occurrence of the process in the short-chain mode, were studied.     

Cosmic γ-ray bursts: Observations and modeling

It is now commonly accepted that cosmic γ-ray bursts (GRBs) are of cosmological origin. This conclusion is based on the statistical analysis of GRBs and the measurements of line redshifts in GRB optical afterglows, i.e., in the so-called long GRBs. In this review, the models of radiation and models of GRB sources are considered. In most of these models, if not in all of them, the isotropic radiation cannot provide the energy release necessary for the appearance of a cosmological GRB. No correlation is noted between the redshift, the GRB-spectrum shape, and the total detected energy. The comparison between data obtained in the Soviet experiment KONUS and the American experiment BATSE shows that they substantially differ in statistical properties and the detection of hard x-ray lines. The investigation of hard gamma (0.1–10 GeV) afterglows, the measurement of prompt optical spectra during the GRB detection, and the further investigation of hard x-ray lines is of obvious importance for gaining insight into the GRB origin. Observations of two bright optical GRB afterglows point to the fact that an initially bright optical flare is directly related to the GRB itself, and the subsequent weak and much more continuous optical radiation is of a different nature. The results of observations of optical GRB afterglows are discussed. They point to the fact that the GRBs originate in distant galaxies with a high matter density, where intense star formation takes place. The interaction of the cosmological GRB radiation with a dense surrounding molecular cloud results in the appearance of long-duration (up to 10 years) weak optical afterglows associated with the heating and reradiation of gas. Results of 2D numerical simulation of the heating and reradiation of gas in various variants of the relative disposition of GRB and molecular clouds are presented. In conclusion, the possible relation between the so-called short GRBs and recurrent sources of soft γ rays in our Galaxy, the so-called “soft gamma repeaters,” is discussed.     

Elektrische Charakterisierung von Hochfrequenz-Niederdruck-Gasentladungen

In recent years there has emerged significant interest in low pressure radio frequency (rf) glow discharges which are used widely particulary in IC fabrication. Various parameters of the rf glow discharge have been found to be useful for its electrical characterization; however, there is no uniformity and agreement. Extensive experimental investigations on various discharge systems have shown, that the self-bias on the rf driven electrode, the complex conductivity and the breakdown characteristic are preferable parameters of rf discharges. Advantageously the self-bias and the complex conductivity should be presented in dependence on the pressure and the applied rf voltage. The discharge current cannot be measured quite accurately due to currents via leaky capacitors and the deviations from a sinusoidal form of the current due to nonlinearities.