Rotating ring-disk electrode studies of the reaction of stable radical cations with styrene and isobutyl vinyl ether

An electroanalytical technique has been utilized in a new method for the study of reactive intermediates in polymerization reactions. A ring-disk electrode system generated persistent carbocation radicals whose stability decreased in the order: 1,3,6,8-tetraphenylpyrene (TPP), rubrene (Ru), 9,10-diphenylanthracene (DPA), and 9,10-dimethylanthracene (DMA). Radical cations from these parent compounds flowed to a collecting ring which was controlled potentiostatically to reduce unreacted cations. When styrene or isobytyl vinyl ether was added to the solution, the concentration of carbocation radicals reaching the electrode was reduced. Current collection efficiencies N were determined as a function of rotation speed ω for each monomer concentration. Plots of N^?1 as ω^?1 in the absence of monomer show no dependence on ω (indicative of stable intermediates), but a linear dependence is found with each concentration of monomer. This indicates a first-order dependence on radical cation concentration. The rate constants show a trend in cation reactivities which is in agreement with that obtained by other methods. This technique, however, extends the range of investigation to a much shorter time scale.     

A new microwave plasma at atmospheric pressure

Plasma at atmospheric pressure can be obtained by surface wave propagation with a surfatron. If the plasma is produced within a quartz tube, it is constricted to a diameter of approx. 1 or 2 mm but its length can attain some tens of centimeters with microwave power as low as 100 W. This plasma is quite uniform along the axis, with a typical electron density of 3 × 10¹⁴ electrons/cm³. Since the excitation and gas temperatures are lower than 4000 K, the plasma is far from local thermodynamic equilibrium. High stability and repeatability is achieved with an argon flow of 0.2–17 l/min. Applications are foreseen in the field of optical spectroscopy and plasma chemistry.     

Synthesis, crystal structure and reactivity of uranium(IV) complexes with p-tert-butylcalix[4]arene ligands

Reactions of UCl4 with 25,27-dimethoxy-5,11,17,23-tetra-tert-butylcalix[4]arene (H2Me2calix) in THF or pyridine at 80 degrees C gave [UCl2(Me2calix)L2] [L = THF (1) or pyridine (2)]. Similar treatment of U(acac)(4) (acac = MeCOCHCOMe) with H2Me2calix in THF or pyridine afforded [U(acac)2(Me2calix)] (3). The bis-calixarene compound [U(Me2calix)(H2calix)] (4) was obtained by reaction of U(OTf)4 or U(OTf)3 with H2Me2calix in pyridine at 110 degrees C. Treatment of UCl4 with H2Me2calix in pyridine at 110 degrees C gave [Mepy][UCl2(Hcalix)(py)2] (5) resulting from demethylation and acid cleavage of the methoxy groups of the calixarene ligand of 2. Adventitious traces of air were responsible for the formation of [Hpy][Mepy]4[{UCl(calix)}3(mu3-O)][UCl6] (6) during the reaction of UCl4 and H2Me2calix, and of [{U(Me2calix)(mu3-O)LiCl(THF)}2] (7) during the reaction of 2 with tBuLi. The X-ray crystal structures of 1.2THF, 2.2py, 3.0.25L (L = THF and py), 4.2py, 5, 6.3py and 7.THF have been determined.     

Multiscale laminar flows with turbulentlike properties

By applying fractal electromagnetic force fields on a thin layer of brine, we generate steady quasi-two-dimensional laminar flows with multiscale stagnation point topology. This topology is shown to control the evolution of pair separation (Delta) statistics by imposing a turbulentlike locality based on the sizes and strain rates of hyperbolic stagnation points when the flows are fast enough, in which case Delta(2) approximately t(gamma) is a good approximation with gamma close to 3. Spatially multiscale laminar flows with turbulentlike spectral and stirring properties are a new concept with potential applications in efficient and microfluidic mixing.     

On Morita Equivalence for Simple Generalized Weyl Algebras

We give a necessary condition for Morita equivalence of simple Generalized Weyl algebras of classical type. We propose a reformulation of Hodges’ result, which describes Morita equivalences in case the polynomial defining the Generalized Weyl algebra has degree 2, in terms of isomorphisms of quantum tori, inspired by similar considerations in noncommutative differential geometry. We study how far this link can be generalized for n ≥ 3.     

A moment inequality of the Marcinkiewicz–Zygmund type for some weakly dependent random fields

The goal of this note is to give a new moment inequality for sums of some weakly dependent random fields. Our result extends moment bounds given by Wu (2007) or Liu and Lin (2009) for causal autoregressive processes and follows by using recursive applications of the Burkhölder inequality for martingales.     

Well-posedness of a degenernate parabolic equation issuing from two-dimensional perfect fluid dynamics

A degenerate parabolic equation of convection-diffusion type has been proposed by Robert and Sommeria in [12] to describe the relaxation towards statistical equilibrium states in 2D incompressible perfect fluid dynamics. The paper is concerned with the Cauchy problem for this equation. The local existence of a variational soluation is obtained in using the decrease of the (negative) mixing entropy and Schauder theorem. A smoothing effect is used when proving the uniqueness of the variational solutions by youdovitch's method. Finally, global existence of solutions and their asymptotic convergence towards Gibbs states are shown for a large class of initial data.     

Einstein-Weyl structures on lightlike hypersurfaces

We study Weyl structures on lightlike hypersurfaces endowed with a conformal structure of certain type and specific screen distribution: the Weyl screen structures. We investigate various differential geometric properties of Einstein-Weyl screen structures on lightlike hypersurfaces and show that, for ambient Lorentzian space ? ₁ ⁿ⁺² and a totally umbilical screen foliation, there is a strong interplay with the induced (Riemannian) Weyl-structure on the leaves.     

A spatial scan statistic for case event data based on connected components

We propose a new spatial scan statistic based on graph theory as a method for detecting irregularly-shaped clusters of events over space. A graph-based method is proposed for identifying potential clusters in spatial point processes. It relies on linking the events closest than a given distance and thus defining a graph associated to the point process. The set of possible clusters is then restricted to windows including the connected components of the graph. The concentration in each of these possible clusters is measured through classical concentration indices based on likelihood ratio and also through a new concentration index which does not depend on any alternative hypothesis. These graph-based spatial scan tests seem to be very powerful against any arbitrarily-shaped cluster alternative, whatever the dimension of the data. These results have applications in various fields, such as the epidemiological study of rare diseases or the analysis of astrophysical data.