Reactions of models of the growth center during anionic polymerization of methacrylate esters

Reactions of α-lithioisobutyric acid esters were studied as models of partial reaction taking place during anionic polymerization of methacrylate esters. The rates of selfcondensation reactions and condensations with nonmetalated esters were determined for these models. In both cases ketoesters were the final products. Besides esters of α,α,α′-trimethylglutaric acid expected according to Michael's reaction scheme the addition of methacrylate esters to α-lithio esters also yielded oligomeric compounds due to repeated addition of methacrylate esters. The α-lithio oligomers of methacrylate esters underwent cyclization condensation which gave rise to esters of substituted cyclohexanonedicarboxylic acids. The alkali metal alkoxides slowed down all the condensation reactions of α-lithio esters investigated here. Such effect of alkoxides also appeared in the cyclization condensation of compounds formed by repeated addition of methacrylate esters, because in the presence of alkoxides the reaction mixture contained a higher amount of higher molecular weight compounds than in a system without alkoxide. The effect of alkoxides observed here is in accordance with the view that the cyclization condensation is one of the termination reactions of the anionic polymerization of methacrylate esters.     

Metallo esters. VII. Stabilizing effect of sodium tert-butoxide on the growth center in the anionic polymerization of methacrylic esters

The growth center in the anionic polymerization of methacrylic esters is stabilized with alkaline alkoxides, sodium tert-butoxide in particular. The lifetime of the growth center was investigated in the polymerization of methyl methacrylate by evaluating yield and molecular weight distribution of the polymer formed when the monomer was added in two doses. The average lifetime of the original growth center stabilized by sodium tert-butoxide at 20°C under the given conditions was longer than several minutes. The stabilization of the growth center was also used in the stepwise copolymerization of n-butyl methacrylate and methyl methacrylate. The copolymer thus obtained in high yield was characterized as a block copolymer on the basis of its solubility, nuclear magnetic resonance (NMR) spectra, and measurements of the complex shear modulus.     

Tautomerism in monothio-β-diketones studied by PMR and quantum chemical calculations

It is shown by proton NMR and quantum chemical PCILO calculations that monothio-β-ketones

in solution exist as different isomers depending on substituents, solvent and temperature. In solvents with low dielectric constants the hydrogen-bridged cis enol form predominates, and is in fast equilibrium (in the NMR scale) with nonchelated trans enol forms down to ?100°C at least. Transition enthalpies are of the order of 7–15 kJ mol^?1. In compounds with R₂ = Me the rotation of the Me -CS group around the neighbouring C-C- bond can be detected and the thermodynamic and kinetic parameters estimated. The reason for the slowing down of this rotation, inferred from the line broadening in NMR, is probably the stabilization of a trans isomer by interaction between the protons of the methyl group and the lone pairs of the oxygen atom. There are no indications for the presence of chelated and non-chelated enethiol isomers from the PMR studies and quantum chemical calculations performed.     

Determination of tobacco alkaloids in single plant cells by capillary electrophoresis

A new capillary electrophoresis system with direct UV detection for the analysis of the tobacco alkaloids nicotine, nornicotine and anabasine in plant microsamples was developed. An electrolyte containing a high concentration of citric acid to provide good buffer capacity at pH 3.6 was found to be most suitable in terms of sensitivity and separation efficiency. At this low pH the tobacco alkaloids are present in cationic form, showing high mobility and increased UV absorption. This system was used for the analysis of nicotine in single epidermal leaf cells of tobacco plants. Only vacuolar concentrations of nicotine were determined, as the vacuole occupies >95% of the entire volume in epidermal cells. The procedure of sample acquisition and preparation for nicotine analysis of vacuolar samples in the pl range is shown. The results indicate a gradient of nicotine from the leaf base to the tip with higher concentrations present in the cells at the tip. Compared to simultaneously measured bulk leaf samples containing all types of cells, tissues and compartments, the concentrations in epidermal cells are much higher. As nicotine is the major defence substance against insects in tobacco and the epidermis is the most exposed leaf tissue this result is physiologically plausible.     

Isotope shift of182Hg and an update of nuclear moments and charge radii in the isotope range181Hg-206Hg

The technique of collinear fast-beam laser spectroscopy has been used to measure the isotope shifts of the even-even isotopes of Hg (Z=80) in the mass range 182≤A≤198 at the on-line mass separator ISOLDE at CERN. The atomic transition studied (6s 6p ³ P ₂- 6s7s ³ S ₁,λ=546.1 nm) starts from a metastable state, which is populated in a quasi resonant charge transfer process. The resulting changes in nuclear mean square charge radii show clearly that¹⁸²Hg follows the trend of the heavier, even, weakly oblate isotopes. Correspondingly the huge odd-even shape staggering in the light Hg isotopes continues and the nuclear shape staggering and shape coexistence persists down to the last isotope investigated,¹⁸¹Hg. An update of isotope shift and hyperfine structure data for^181–206Hg is given, with a revised evaluation of the differences in nuclear mean square charge radii and of spectroscopic quadrupole moments.     

Statistical verification of crystallization in hard sphere packings under densification

The performance of various structure characteristics in the task of indicating structural peculiarities in packings of hard spheres is investigated. Various characteristics based on Voronoi polyhedra, spherical harmonics, and Delaunay simplices are considered together with the pair correlation function and the mean number of r-close triples. They are applied to a set of hard sphere packings of density φ from 0.62 to 0.72. It turns out that all used structure characteristics are able to indicate changes of order from non-crystalline to crystalline packings. However, not all of them are sensitive enough to indicate different stages of structure transformation under densification. The characteristics based on Delaunay simplices turn out to be the most sensitive for this purpose. For the models considered three principal structure classes are found: packings of densities lower than the known critical value 0.64 showing a non-crystalline behavior; packings with considerable crystalline regions for φ up to 0.66–0.67; rather complete crystals although with numerous defects for φ above 0.67.     

An Analysis of the Transition Zone Between the Various Scaling Regimes in the Small-World Model

We analyse the so-called small-world network model (originally devised by Strogatz and Watts), treating it, among other things, as a case study of non-linear coupled difference or differential equations. We derive a system of evolution equations containing more of the previously neglected (possibly relevant) non-linear terms. As an exact solution of this entangled system of equations is out of question we develop a (as we think, promising) method of enclosing the “exact” solutions for the expected quantities by upper and lower bounds, which represent solutions of a slightly simpler system of differential equation. Furthermore we discuss the relation between difference and differential equations and scrutinize the limits of the spreading idea for random graphs. We then show that there exists in fact a “broad” (with respect to scaling exponents) crossover zone, smoothly interpolating between linear and logarithmic scaling of the diameter or average distance. We are able to corroborate earlier findings in certain regions of phase or parameter space (as e.g. the finite size scaling ansatz) but find also deviations for other choices of the parameters. Our analysis is supplemented by a variety of numerical calculations, which, among other things, quantify the effect of various approximations being made. With the help of our analytical results we manage to calculate another important network characteristic, the (fractal) dimension, and provide numerical values for the case of the small-world network.