Investigation of transitions and relaxation processes in polystyrene by using positron annihilation

The glass transition and relaxation processes in polystyrene resins with the number average molecular weight ranging from 7.0·10² to 9.8·10⁴ were studied with the positron annihilation technique. The pick-off annihilation lifetime of ortho-positronium (₃) and its intensity (I ₃) were measured in the temperature range from 20 to 430 K. The glass transition temperature (T _g) was determined as an onset temperature coefficient of ₃.T _g shows the molecular weight dependence in these samples. BelowT _g, local motions were detected by measurements ofI ₃. The local motions could be observed above 100 K in this experiment.I ₃ show the minimum at around 250 K and it does not show molecular weight dependence.     

Nitrosation of Phenolic Substrates under Mildly Basic Conditions: Selective Preparation of p-Quinone Monooximes and Their Antiviral Activities

Nitrosation of 3-methoxyphenol and 1-naphthol were examined under both acidic (NaNO(2)-EtCO(2)H-H(2)O) and basic (i-AmNO(2)-K(2)CO(3)-DMF) conditions. Acidic nitrosations afforded ortho-directed products, whereas para-directed nitrosations were observed under basic conditions to yield p-quinone monooximes. The basic para-directed nitrosation was further examined using 15 phenols, two naphthols, and four phenolic heterocyclics. A one-pot operation of the basic nitrosation followed by methylation with dimethyl sulfate gave the corresponding methyl ethers in high yield. Two p-quinone monooximes derived from 3-methoxyphenol and 8-hydroxyquinoline showed a moderate activity against HSV-1, and the latter oxime was also effective against HSV-2. On the other hand, p-quinone monooximes derived from methyl salicylate, 1-naphthol, 7-hydroxy-2-methylbenzo[b]furan, and 8-hydroxycoumarin showed the comparable activity to that of DDI against HIV-1.     

A twin optically-pumped far-infrared CH3OH laser for plasma diagnostics

A twin optically-pumped far-infrared CH₃OH laser has been constructed for use in plasma diagnostics. The antisymmetric doublet due to the Raman-type resonant two-photon transition is reproducibly observed at 118.8 m. With the 118.8-m line, it is obtained from the frequency separation of the anti-symmetric doublet that CH₃OH absorption line center is 16±1 MHz higher than the pump 9.7-m P(36) CO₂ laser line center. It is shown that the Raman-type resonant two-photon transition is useful in order to get several-MHz phase modulation for the far-infrared laser interferometer. Some preliminary performances of this twin laser for the modulated interferometer are described.This work was carried out under the collaborating research program at the Institute of Plasma Physics, Nagoya University, Nagoya 464, Japan.     

Facile synthesis of optically active oxindoles by copper-catalyzed asymmetric monotosylation of prochiral 1,3-diols

A facile synthetic method toward optically active 3,3-disubstituted oxindoles with excellent enantioselectivity was achieved using chiral copper-catalyzed desymmetrization of prochiral 1,3-diols. The monotosylated product was transformed into oxindole derivatives efficiently.     

Study of relaxation processes in polyethylene and polystyrene by positron annihilation

Relaxation processes in polyethylene (PE) and polystyrene (PS) were studied by positron annihilation technique. For PE, above the glass transition temperature, T_g, the size of free volumes and its concentration were increased by the micro-Brownian motion of molecules. For PS, local motions of molecules in backbone chains were found to start above 260 K. However, these local motions were suppressed by an interphenyl correlation. For both PE and PS, below 250–260 K, the formation probability of positronium atoms increased with decreasing temperature. This fact was assigned to the freezing in of the local motions of molecules. For PS, an onset of the local motions of molecules was observed above 100 K. These motions were expected to be associated with liberation of phenyl groups. © 1996 John Wiley & Sons, Inc.     

Free volumes in polystyrene probed by positron annihilation

Free volume characteristics in three samples of monodisperse polystyrene were investigated by positron annihilation technique over a temperature range from 300 to 380 K. The number-average molecular weight of the samples ranged from 5730 to 1,524,000. The observed lifetime spectra were resolved into three components, where the longest lifetime, τ₃ was associated with the pick-off annihilation of ortho-positronium (o-Ps) trapped by free volumes. The change of the temperature coefficient of τ₃ was observed at around 350 K, at which the value of τ₃ was a constant value of 2,3 ns for all specimens with different molecular weights. There was no discrete change of τ₃ in intensity, which is corresponding to the number of free volumes. The size of free volume at glass transition was evaluated to be 0.l nm³. © 1996 John Wiley & Sons, Inc.     

Projective structures with discrete holonomy representations

Let denote the set of projective structures on a compact Riemann surface whose holonomy representations are discrete. We will show that each component of the interior of is holomorphically equivalent to a complex submanifold of the product of Teichmüller spaces and the holonomy representation of every projective structure in the interior of is a quasifuchsian group.

     

Two-dimensional thermoelastic analysis of a functionally graded cylindrical panel due to nonuniform heat supply

This paper is concerned with the theoretical treatment of the steady-state thermoelastic problem of a functionally graded cylindrical panel due to nonuniform heat supply in the circumferential direction. The thermal and thermoelastic constants of the cylindrical panel are expressed as power functions of the radial coordinate. We obtain the exact solution for the two-dimensional temperature change in a steady state, and thermal stresses of a simple supported cylindrical panel under the state of plane strain. Some numerical results are shown in figures and tables. Furthermore, the influence of the nonhomogeneity of the material, the radius ratio and the span angle upon the temperature change, displacements and stresses is investigated.     

A basic study on the sound field analysis of periodic structures by boundary integral equation method

This study deals with the development of the approximate method to analyze the sound field around equally spaced finite obstacles, using the periodic boundary condition. First, on the assumption that the equally spaced finite obstacles are the periodically arranged obstacles, the sound field is analyzed by boundary integral equation method with a Green’s function which satisfies the periodic boundary condition. Furthermore, by comparing these results and the exact solution by using the fundamental solution as Green’s function, the validity of the approximate method is also investigated. Next, in order to evaluate the applicability of the approximate method, the simple formula using some parameters, i.e., the frequency, the period, and the number of obstacles, etc., is proposed. The results of the sound field analysis applied the formula are presented.     

Aqueous self-aggregates of amphiphilic zinc 3-hydroxy- and 3-methoxy-chlorins for supramolecular light-harvesting systems

Aqueous aggregates of zinc 3¹-hydroxy- and 3¹-methoxy-13¹-oxo-chlorins possessing a hydrophilic tetraoxyethylene chain were prepared. Zinc 3¹-methoxy-chlorin formed a well-ordered aggregate without intermolecular hydrogen bonding which has been widely accepted in most structural models for BChl-c, d, e aggregates in a major light-harvesting antenna of green photosynthetic bacteria, chlorosome.