Ethylene/1‐hexene copolymerization with tetramethyldisiloxane‐bridged bis(indenyl) metallocenes

Ethylene/1‐hexene copolymerizations with disiloxane‐bridged metallocenes, rac‐ and meso‐1,1,3,3‐tetramethyldisiloxanediyl‐bis(1‐indenyl)zirconium dichloride (rac‐ 1 , meso‐ 1 ) activated by modified methylaluminoxane were performed to investigate the influence of conformational dynamics on comonomer selectivity. Although ¹H NOESY (nuclear Overhauser and exchange spectroscopy) analysis indicated that the most stable conformation for the meso isomer in solution was that in which both indenes project over the metal coordination site, this isomer showed higher 1‐hexene selectivity in copolymerization (r_e = 140 ± 30, r_h = 0.024 ± 0.004) than the rac isomer with only one indene over the coordination site (r_e = 240 ± 20, r_h = 0.005 ± 0.001). The meso isomer showed high 1‐hexene selectivity, a high product of reactivity ratios (r_er_h = 3.3 ± 0.5) and produced copolymers that could be separated into fractions with different ethylene content suggesting that the active species exhibited multisite behavior and populated conformations with different comonomer selectivities during the copolymerization. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3323–3331, 2004     

Pointwise and L2 bounds in some nonstandard problems for the heat equation

We consider some initial-boundary value problems for the linear and nonlinear heat equation where the gradient of the solution is prescribed on the boundary. Assuming that a solution exists, we obtain bounds for the solution and its gradient by maximum principle arguments or by means of differential and integral inequalities.     

The magnetism of rare earth intermetallics RFe4Al8

Hyperfine Interactions - The YFe4Al8 and ErFe4Al8 intermetallics were studied by57Fe Mössbauer spectroscopy between 2 K and room temperature. The spectra are consistent with iron occupying 8f...     

Electrochemical Properties of Poly-3-methylthiophene Films: A Cyclic Voltammetry and Chronoamperometry Study

The charge transfer in poly-3-methylthiophene films in 0.05–0.5 M LiClO₄ solutions in acetonitrile is studied by cyclic voltammetry and chronoamperometry. An analysis of data on the current relaxation following a film perturbation by a low-voltage pulse reveals two constituents of the current relaxation, both exponentially dependent on time. Dependence of parameters of the empirical equation derived for the current relaxation on experimental variables is studied.     

Dynamic supercoiling bifurcations of growing elastic filaments

Certain bacteria form filamentous colonies when the cells fail to separate after dividing. In Bacillus subtilis, Bacillus thermus, and Cyanobacteria, the filaments can wrap into complex supercoiled structures as the cells grow. The structures may be solenoids or plectonemes, with or without branches in the latter case. Any microscopic theory of these morphological instabilities must address the nature of pattern selection in the presence of growth, for growth renders the problem nonautonomous and the bifurcations dynamic. To gain insight into these phenomena, we formulate a general theory for growing elastic filaments with bending and twisting resistance in a viscous medium, and study an illustrative model problem: a growing filament with preferred twist, closed into a loop. Growth depletes the twist, inducing a twist strain. The closure of the loop prevents the filament from unwinding back to the preferred twist; instead, twist relaxation is accomplished by the formation of supercoils. Growth also produces viscous stresses on the filament which even in the absence of twist produce buckling instabilities. Our linear stability analysis and numerical studies reveal two dynamic regimes. For small intrinsic twist the instability is akin to Euler buckling, leading to solenoidal structures, while for large twist it is like the classic writhing of a twisted filament, producing plectonemic windings. This model may apply to situations in which supercoils form only, or more readily, when axial rotation of filaments is blocked. Applications to specific biological systems are proposed.     

Arithmetic functions with linear recurrence sequences

We obtain asymptotic formulas for all the moments of certain arithmetic functions with linear recurrence sequences. We also apply our results to obtain asymptotic formulas for some mean values related to average orders of elements in finite fields.