Polydispersity effects on diffusion in polymers: Concentration profiles of d-polystyrene measured by forward recoil spectrometry

Forward recoil spectrometry is shown to be a useful technique for measuring diffusion of d-polymer chains in h-polymer melts. Concentration profiles of a deuterated diffusing species may be determined with a depth resolution of 80 nm and a sensitivity of 0.1 vol % d-polymer in h-polymer. Consequently diffusion coefficients as small as 10^?16 cm²/s can be readily measured. If polymer chains diffuse by a reptation mechanism, the concentration profile ø(x) of diffusing polydisperse polymer should be quite different from ø_m(x), the Fickian solution, which one obtains for monodisperse polymer. This idea was tested by measuring ø(x) of polydisperse d-polystyrene (d-PS) diffusing into h-PS. The results are in excellent agreement with the ø(x) predicted from the reptation model and the experimentally determined molecular weight distribution.     

The Lebesgue Constant for Higher Order Hermite-Fejér Interpolation on the Chebyshev Nodes

For a fixed integer m ≥ 0, and for n = 1, 2, 3, ..., let λ_{2m, n}(x) denote the Lebesgue function associated with (0, 1,..., 2m) Hermite-Fejér polynomial interpolation at the Chebyshev nodes {cos[(2k−1) π/(2n)]: k=1, 2, ..., n}. We examine the Lebesgue constant Λ_{2m, n} max{λ_{2m, n}(x): −1 ≤ x ≤ 1}, and show that Λ_{2m, n} = λ_{m, n}(1), thereby generalising a result of H. Ehlich and K. Zeller for Lagrange interpolation on the Chebyshev nodes. As well, the infinite term in the asymptotic expansion of Λ_{2m, n)} as n → ∞ is obtained, and this result is extended to give a complete asymptotic expansion for Λ_{2, n}.     

Overtone spectra and anharmonic resonances in haloacetylenes

In this work preliminary results are reported on an extensive vibrational analysis of the molecules HCCX and DCCX with X = F and Cl, in which a number of anharmonic resonances are analysed. The importance of quartic anharmonic resonances in these molecular types is reported involving the effective constants K₁₂₄₄ and K₁₂₅₅, and these are related to the corresponding resonances in acetylene and its isotopomers. The correct analysis of Fermi resonances and quartic anharmonic resonances is important not only in reproducing the high overtone energy levels, but also in fitting the observed rotational constants, and in determining the _r constants and hence the equilibrium rotational constants. In this paper we revise our recent analysis of the equilibrium structure of HCCF in the light of these effects.     

Positron mobility in anthracene

We have measured the positron mobility in a sample of scintillation grade anthracene at two temperatures. We obtain at 300 K: =(26.0±0.9±2.6) cm²V^–1s^–1 and at 77 K: =(33.4±1.1±3.3) cm²V^–1s^–1, where the first error estimate is statistical and the second is systematic. We have also made preliminary measurements on a highly purified sample that yields =(130±3±20) cm² V^–1 s^–1 at 300 K. The data are consistent with the hypothesis that the positron is scattered from both impurities and acoustic phonons in the first sample, and predominantly from photons in the second. It appears that positrons in pure anthracene crystals are delocalized and have a mean free path of about 85 Å at room temperature.     

An intelligence ink for oxygen

A generic ink formulation is described, comprising semiconductor photocatalyst particles, a brightly-coloured redox dye, a mild reducing agent, a polymer and a solvent, that creates an irreversible, reusable, UV-light-activated, colorimetric indicator or intelligence ink for oxygen.     

Erythrocyte electrokinetic behavior under low ionic strength conditions

Under low ionic strength conditions, a linear approximation of the electrostatic potential within the charged polyelectrolyte layer coating the membrane bilayer leads to overestimation of the red cell electrokinetic mobility. Considering the full non linearized Poisson-Boltzmann and Navier-Stokes equations relative to the erythrocyte system, the deviation at low ionic strength between theoretical and experimental values for the cell mobility then almost disappears. A weak glycocalyx expansion may account for the remaining differences. However, this result is in contrast with previously suggested explanations involving an important stretching of the polyelectrolyte chains to interpret the “artificial” erythrocyte aggregation at low ionic strength. Under such conditions cell aggregation is probably induced by haemolysate adsorption onto the erythrocyte membrane and is unlikely to be the consequence of a strong interfacial rearrangement.     

Reactions of carbon dioxide with metal carbonyl anions

The reactivity of a series of metal carbonyl anions with CO₂ has been found to parallel their relative nucleophilicities. The highly nucleophilic species, C₅H₅Fe(CO)^?₂, reacts readily to give the dimer, (C₅H₅Fe(CO)₂)₂, and carbonate while Co(CO)^?₄ is unreactive. The reaction of ¹³CO₂ with C₅H₅Fe(CO)^?₂ results in the formation of the ¹³CO enriched dimer.