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     

Some remarks on Newton–Sabatier methods

It is shown how Newton–Sabatier methods (arising in inverse scattering at fixed energy) can be related to spectral measures and typically when they correspond to regular potentials. A number of spectral formulae for various transmutation kernels are also given in terms of general Kontorovi?–Lebedev theory and connections to generating functions, generalized orthogonal polynomials, etc. are indicated.     

Microstructure array on Si and SiOx generated by micro-contact printing, wet chemical etching and reactive ion etching

A method, combining micro-contact printing (μCP), wet chemical etching and reactive ion etching (RIE), is reported to fabricate microstructures on Si and SiOx. Positive and negative structures were generated based on different stamps used for μCP. The reproducibility of the obtained microstructures shows the methodology reported herein could be useful in Micro-Electro-Mechanical Systems (MEMS), optical and biological sensing applications.     

Colliding stacks: A large deviations analysis

We analyze the performance of a prototypical scheme for shared storage allocation: two initially empty stacks evolving in a contiguous block of memory of size m. We treat the case in which the stacks are more likely to shrink than grow, but with the probabilities of insertion and deletion allowed to depend arbitrarily on stack height as a fraction of m. New results are obtained on the m → ∞ asymptotics of the stack collision time, and of the final stack heights. The results of Wentzell and Freidlin on the large deviations of Markov chains are used, and the relation of their formalism to the Hamiltonian formulation of classical mechanics is emphasized. Certain results on higher-order asymptotics follow from WKB expansions.     

Optimality relationships forp-cyclic SOR

Summary The optimality question for blockp-cyclic SOR iterations discussed in Young and Varga is answered under natural conditions on the spectrum of the block Jacobi matrix. In particular, it is shown that repartitioning a blockp-cyclic matrix into a blockq-cyclic form,q, results in asymptotically faster SOR convergence for the same amount of work per iteration. As a consequence block 2-cyclic SOR is optimal under these conditions.Research supported in part by the US Air Force under Grant no. AFOSR-88-0285 and the National Science Foundation under grant no. DMS-85-21154 Present address: Boeing Computer Services, P.O. Box 24346, MS 7L-21, Seattle, WA 98124-0346, USA     

Transfer of near-infrared monochromator calibrations for tobacco constituents to tilting-filter instruments

Near-infrared calibrations for water, reducing sugar, glycerin, propylene glycol, nicotine, and menthol in tobacco blends were first obtained with a monochromator instrument. Transfer of calibrations to a tilting-filter instrument for factory trials is shown to be facilitated greatly by the computer-assisted scheme MTRAN. By means of this software, calibration equations were established for a Neotec 51A instrument that is sufficiently rugged for factory use. The predictive capabilities of the transferred calibrations are similar to those of the research monochromator.     

The existence of smooth densities for the prediction filtering and smoothing problems

The qualitative behavior of buckled states of two different models of elastic beams is studied. It is assumed that random imperfections affect the governing nonlinear equations. It is shown that near the first critical value of the buckling load the stochastic bifurcation is described asymptotically by an algebraic equation whose coeffficients are Gaussian random variables. The corresponding asymptotic expansion for the displacement is to lowest order a Gaussian stochastic process.Work supported by NSF Grant No. DCR81-14726.Work supported by NSF Grant No. DMS87-01895.     

Limits of parallelism in explicit ODE methods

Numerical methods for ordinary initial value problems that do not depend on special properties of the system are usually found in the class of linear multistage multivalue methods, first formulated by J.C. Butcher. Among these the explicit methods are easiest to implement. For these reasons there has been considerable research activity devoted to generating methods of this class which utilize independent function evaluations that can be performed in parallel. Each such group of concurrent function evaluations can be regarded as a stage of the method. However, it turns out that parallelism affords only limited opportunity for reducing the computing time with such methods. This is most evident for the simple linear homogeneous constant-coefficient test problem, whose solution is essentially a matter of approximating the exponential by an algebraic function. For a given number of stages and a given number of saved values, parallelism offers a somewhat enlarged set of algebraic functions from which to choose. However, there is absolutely no benefit in having the degree of parallelism (number of processors) exceed the number of saved values of the method. Thus, in particular, parallel one-step methods offer no speedup over serial one-step methods for the standard linear test problem. Although the implication of this result for general nonlinear problems is unclear, there are indications that dramatic speedups are not possible in general. Also given are some results relevant to the construction of methods.Work supported in part by National Science Foundation grants DMS 89 11410 and DMS 90 15533 and by US Department of Energy grant DOE DEFG02-87ER25026. Work of the second author was completed while at the University of Illinois.