Local chain‐configuration dependence of the mechanisms of the chemical reaction of poly(vinyl chloride). IX. Novel results on stereoselectivity of chlorination reaction

A poly(vinyl chloride) (PVC) sample was chlorinated in solution in the presence of 2,2′‐azobisisobutyronitrile and by the fluid‐bed method. The aim was to evaluate the scope of the stereoselectivity of the chlorination reaction. The quantitative microstructural analysis of the residual PVC with a degree of chlorination was followed by ¹³C NMR spectroscopy. From the evolution of the content of isotactic (mm), heterotactic (mr), and syndiotactic (rr) triads and of mmmm, mmmr, and rmmr isotactic pentads in the unchlorinated parts of the polymer, it was unambiguously inferred that the chlorination reaction proceeds by a stereoselective mechanism in that the mr heterotactic triads are the most reactive structures followed by the isotactic triad at mmmr and rmmr pentads. This conclusion was confirmed on the basis of the Fourier transform infrared results. The results provide valuable information regarding the effect of tacticity and related local conformations in the chemical reactions of PVC. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 508–519, 2003     

Nickel as a chemical modifier for sensitivity enhancement and fast atomization processes in electrothermal atomic absorption spectrometric determination of cadmium in biological and environmental samples.

A systematic study of the efficiency of protons, Ni, Pd and Th as chemical modifiers for the determination of cadmium by electrothermal atomic absorption spectrometry (ETAAS) using fast temperature programs was made for platform atomization. A comparison was made in terms of the salt type, absorbance-time profiles and elimination of the sodium chloride interference. The results were adapted to develop a method for the ETAAS determination of cadmium in biological and environmental samples. The highest sensitivity to determine cadmium in biological and environmental samples was obtained using nickel (together with protons) as a chemical modifier. The accuracy of the method was tested by the determination of cadmium in different certified reference materials. The best detection limit and the characteristic mass of Cd were found to be 0.03 ng mL(-1) and 0.35 pg, respectively.     

Gas Concentration in Industrial Emissions Retrieved from a Laser-Beam Aureole

The feasibility of reconstructing components of industrial emissions by a remote method is studied under conditions of strong laser radiation scattering. It is demonstrated that an aureole around the laser beam bears information on optical parameters of the medium. Formulas for calculating the extinction coefficient of the medium and the concentration of the desired gas component in the emission from the measured radial profile of aureole brightness are derived.     

Classification of the energy levels of the cyclopentane molecule

The energy levels of the cyclopentane molecule are classified taking into account pseudorotation and inversion motion caused by the nonplanarity of the equilibrium configuration of the five-membered cycle of the carbon nuclei of the molecule. For this purpose, the relatively recently developed symmetry-group chain methods, which are the most powerful methods at present, are used.     

Potential barrier in the problem of the evolution of a dinuclear system

A method for calculating the potential energy of a dinuclear system evolving along the charge-asymmetry coordinate is analyzed. It is shown that the shape of the potential is determined primarily by the dependence of the proton separation energy on the mass and the charge number of nuclei that form the dinuclear system and by the concerted effect of the Coulomb fields of these nuclei on the single-particle motion of constituent nucleons.     

Synthesis and characterization of poly(methyl methacrylate)‐block‐poly(methylphenylsilane)‐ block‐poly(methyl methacrylate) by atom transfer radical polymerization

ABA block copolymers of methyl methacrylate and methylphenylsilane were synthesized with a methodology based on atom transfer radical polymerization (ATRP). The reaction of samples of α,ω‐dihalopoly(methylphenylsilane) with 2‐hydroxyethyl‐2‐methyl‐2‐bromoproprionate gave suitable macroinitiators for the ATRP of methyl methacrylate. The latter procedure was carried out at 95 °C in a xylene solution with CuBr and 2,2‐bipyridine as the initiating system. The rate of the polymerization was first‐order with respect to monomer conversion. The block copolymers were characterized with ¹H NMR and ¹³C NMR spectroscopy and size exclusion chromatography, and differential scanning calorimetry was used to obtain preliminary evidence of phase separation in the copolymer products. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 30–40, 2003     

Schemes for preparation of W-and GHZ-class states from atoms and atomic ensembles

Independent systems, each containing an atomic ensemble entangled through the interaction with its own photon, can be, in turn, entangled in the course of measurements. Schemes for preparing states of the W and Greenberger-Horne-Zeilinger (GHZ) classes with the use of projective measurements of light that include three-photon parametric interactions are proposed and analyzed.