A Close-to-Aromatize Approach for the Late-Stage Functionalization through Ring Closing Metathesis

An efficient approach for the synthesis of monosubstituted aromatic compounds relying on a ring-closing metathesis followed by spontaneous 1,2-elimination is presented. The efficiency for late-stage functionalization is highlighted in various solvents (up to 920 TON). This approach is compatible with strained cycles and other multiple bonds in the substrate.     

Finite difference modeling of the gas transport process in glassy polymers

Finite difference modeling has been used to predict the results of gas transport experiments for a concentration-dependent diffusion coefficient. Experiments on the transport of CO₂ in poly(ethylene terephthalate) and poly(ethylene naphthalate) had previously shown a difference between the effective diffusion coefficients for absorption and desorption runs of a double-sided experiment, but this effect had not been seen for single-sided experiments. The finite difference calculations show that such results are to be expected, and the parameters included in the models that attempt to describe the diffusion process in glassy polymers, such as the dual-mode model, and which lead to concentration-dependent diffusion coefficients, can be found by fitting the experimental data for the double-sided experiment using finite difference modeling. The dependence of the effective diffusion coefficient on pressure for the single-sided experiment can be correctly predicted using results from the double-sided experiment for an identical sample. © 1996 John Wiley & Sons, Inc.     

Recent developments in the science and technology of high modulus flexible polymers

Recent progress in basic science and technological innovation is described for three areas of research in the IRC at Leeds University; melt spun high modulus polyethylene fibres, hydrostatic extrusion and die drawing.     

Kaon production in\bar pp interactions at c.m. energies from 200 to 900 GeV

A detailed analysis ofK _s ⁰ production in \(\bar pp\) |<2.5 the average transverse momentum is found to be 0.53±0.07 GeV/c at 200 GeV and 0.62±0.08 GeV/c at 900 GeV, which is an increase with respect to data at c.m. energies below 60 GeV. TheK _s ⁰ production cross sections in inelastic collisions are 29±4 mb at 200 GeV and 63±6 mb at 900 GeV, showing an increase compared to lower energy data. The central kaon density is found to increase as a logarithmic function of energy. At 900 GeV, where statistics are sufficient to allow one to draw conclusions, the average transverse momentum is higher in events with large charged multiplicity than in events with low multiplicity.     

Recent results from the TCV tokamak

During the first two years of operation, the TCV tokamak has produced a large variety of plasma shapes and magnetic configurations, with 1.0B _tor1.46T,I _p800kA,k2.05, –0.71. A new shape control algorithm, based on a finite element reconstruction of the plasma current in real time, has been implemented. Vertical growth rates up to 1000s^–1 have been stabilized using the external coil system. Ohmic H-modes with Troyon factors ( _tor aB/I _p) up to two and densities up to 2.25×10²⁰m^–3, corresponding to the Greenwald limit, have been obtained in diverted discharges. Limiter H-modes with line averaged electron densities up to 1.7×10²⁰m^–3 have been obtained in elongated D-shaped plasmas with 360 kAI _P600 kA.Presented at 17^th Symposium Plasma Physics and Technology, Prague, June 13–16, 1995.This work was partly supported by the Fonds National Suisse de la Recherche Scientifique.     

Eliminating Indeterminacy in Singularly Perturbed Boundary Value Problems with Translation Invariant Potentials

Solutions exhibiting an internal layer structure are constructed for a class of nonlinear singularly perturbed boundary value problems with translation invariant potentials. For these problems, a routine application of the method of matched asymptotic expansions fails to determine the locations of the internal layer positions. To overcome this difficulty, we present an analytical method that is motivated by the work of Kath, Knessl and Matkowsky [4]. To construct a solution having n internal layers, we first linearize the boundary value problem about the composite expansion provided by the method of matched asymptotic expansions. The eigenvalue problem associated with the homogeneous form of this linearization is shown to have n exponentially small eigenvalues. The condition that the solution to the linearized problem has no component in the subspace spanned by the eigenfunctions corresponding to these exponentially small eigenvalues determines the internal layer positions. These “near” solvability conditions yield algebraic equations for the internal layer positions, which are analyzed for various classes of nonlinearities.     

Large-time asymptotics for the Gt/Mt/st+GIt many-server fluid queue with abandonment

We previously introduced and analyzed the G _t /M _t /s _t +GI _t many-server fluid queue with time-varying parameters, intended as an approximation for the corresponding stochastic queueing model when there are many servers and the system experiences periods of overload. In this paper, we establish an asymptotic loss of memory (ALOM) property for that fluid model, i.e., we show that there is asymptotic independence from the initial conditions as time t evolves, under regularity conditions. We show that the difference in the performance functions dissipates over time exponentially fast, again under the regularity conditions. We apply ALOM to show that the stationary G/M/s+GI fluid queue converges to steady state and the periodic G _t /M _t /s _t +GI _t fluid queue converges to a periodic steady state as time evolves, for all finite initial conditions.     

Mass separator for radioactive isotopes

A new isotope separator has been designed, constructed, and put into routine operation for separation of ¹³³Xe providing a major advancement and significant cost reduction in preparation of this radioactive isotope. The design features and advantages are discussed that expedite high purity separation of relatively small quantities of this isotope. These advantages could be easily used to expedite separation of other shorter-lived radioactive isotopes.     

Synthesis and Properties of 2,3-Diethynyl-1,3-Butadienes

The first general preparative access to compounds of the 2,3-diethynyl-1,3-butadiene (DEBD) class is reported. The synthesis involves a one-pot, twofold Sonogashira-type, Pd⁰-catalyzed coupling of two terminal alkynes and a carbonate derivative of a 2-butyne-1,4-diol. The synthesis is broad in scope and members of this structural family are kinetically stable enough to be handled using standard laboratory techniques at ambient temperature. They decompose primarily through heat-promoted cyclodimerizations, which are impeded by alkyl substitution and accelerated by aryl or alkenyl substitution. An iterative sequence of these unprecedented Sonogashira-type couplings generates a new type of expanded dendralene. A suitably substituted DEBD carrying two terminal alkyne groups undergoes Glaser–Eglinton cyclo-oligomerization to produce a new class of expanded radialenes, which are chiral due to restricted rotation about their 1,3-butadiene units. The structural features giving rise to atropisomerism in these compounds are distinct from those reported previously.