Dielectric and dynamic mechanical relaxation studies on poly(aryl ether ketone)s

The relaxation behavior of four amorphous poly(aryl ether ketone)s was investigated using dielectric relaxation spectroscopy and dynamic mechanical analysis. The temperature dependence of the relaxation times of the glass transition process and the cooperative nature of this process were unaffected by changes in polymer structure. The temperature location of the loss peaks for all polymers progressed smoothly between the low frequency of the mechanical measurements and the higher frequencies of the dielectric probe. Differences were observed in mechanical activation energy and dielectric relaxation strength for one polymer which contained a significant concentration of meta linkages, compared with the para-linked polymers, while relaxation broadness was generally greater in the dynamic mechanical mode. Changes in chemical structure had little effect on the shape, intensity, and location of the β-relaxation peak, the main observation being that the Arrhenius activation energy measured by dynamic mechanical analysis was significantly higher than that calculated from the dielectric data. The dielectric β-relaxation was sensitive to absorbed moisture. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 851–859, 1998     

In situ SIMS analysis and reactions of surfaces prepared by soft landing of mass-selected cations and anions using an ion trap mass spectrometer

Mass-selected polyatomic cations and anions, produced by electrosonic spray ionization (ESSI), were deposited onto polycrystalline Au or fluorinated self-assembled monolayer (FSAM) surfaces by soft landing (SL), using a rectilinear ion trap (RIT) mass spectrometer. Protonated and deprotonated molecules, as well as intact cations and anions generated from such molecules as peptides, inorganic catalysts, and fluorescent dyes, were soft-landed onto the surfaces. Analysis of the modified surfaces was performed in situ by Cs⁺ secondary ion mass spectrometry (SIMS) using the same RIT mass analyzer to characterize the sputtered ions as that used to mass select the primary ions for SL. Soft-landing times as short as 30 s provided surfaces that yielded good quality SIMS spectra. Chemical reactions of the surfaces modified by SL were generated in an attached reaction chamber into which the surface was transferred under vacuum. For example, a surface on which protonated triethanolamine had been soft landed was silylated using vapor-phase chlorotrimethylsilane before being returned still under vacuum to the preparation chamber where SIMS analysis revealed the silyloxy functionalization. SL and vapor-phase reactions are complementary methods of surface modification and in situ surface analysis by SIMS is a simple way to characterize the products produced by either technique.     

Orbits of parabolic subgroups on metabelian ideals

Let k be an algebraically closed field, t∈Z?1, and let B be the Borel subgroup of GLt(k) consisting of upper-triangular matrices. Let Q be a parabolic subgroup of GLt(k) that contains B and such that the Lie algebra qu of the unipotent radical of Q is metabelian, i.e. the derived subalgebra of qu is abelian. For a dimension vector with , we obtain a parabolic subgroup P(d) of GLn(k) from B by taking upper-triangular block matrices with (i,j) block of size di×dj. In a similar manner we obtain a parabolic subgroup Q(d) of GLn(k) from Q. We determine all instances when P(d) acts on qu(d) with a finite number of orbits for all dimension vectors d. Our methods use a translation of the problem into the representation theory of certain quasi-hereditary algebras. In the finite cases, we use Auslander-Reiten theory to explicitly determine the P(d)-orbits; this also allows us to determine the degenerations of P(d)-orbits.     

Forecasting with cue information: A comparison of multiple regression with alternative forecasting approaches

Multiple linear regression (MLR) is a popular method for producing forecasts when data on relevant independent variables (or cues) is available. The accuracy of the technique in forecasting the impact on Greek TV audience shares of programmes showing sport events is compared with forecasts produced by: (1) a simple bivariate regression model, (2) three different types of artificial neural network, (3) three forms of nearest neighbour analysis and (4) human judgment. MLR was found to perform relatively poorly. The application of Theil’s bias decomposition and a Brunswik lens decomposition suggested that this was because of its inability to handle complex non-linearities in the relationship between the dependent variable and the cues and its tendency to overfit the in-sample data. Much higher accuracy was obtained from forecasts based on a simple bivariate regression model, a simple nearest neighbour procedure and from two of the types of artificial neural network.     

Capillary electrophoresis of the scrapie prion protein from sheep brain

Scrapie in sheep and goats causes a progressive, degenerative disease of the central nervous system and is the prototype of other transmissible spongiform encephalopathies (TSE) found in humans and in animals. In samples of TSE-affected brains, unique rod-shaped structures are found and are infectious. These rods are composed of a protease-resistant, post-translationally modified cellular protein (PrP^sc) that has a molecular mass of ca. 27 000 on sodium dodecyl sulfate-polyacrylamide gel electrophoresis. Laboratory tests used for the diagnosis of scrapie detect PrP^sc. The overall concentration of PrP^sc in tissues is low. The present methods to diagnose scrapie are lengthy, require relatively large quantities of starting material to detect PrP^sc and lack sensitivity. We explored the use of free zone capillary electrophoresis and immunocomplex formation to detect PrP^sc in the brain tissue of infected sheep. Brain tissue from both infected (as confirmed by histological and biological tests) and from normal animals was used to prepare the PrP^sc. After treatment with proteinase K and non-ionic detergents, PrP^sc was solubilized and reacted with a rabbit antiserum specific for a peptide of the prion protein. Immunocomplex formation was observed for the samples from scrapie-infected brain but not for samples from normal brain. When a fluorescein-labeled goat anti-rabbit immunoglobulin was used as a second antibody, the detection of immunocomplex formation was enhanced both by the immunological technique and by using laser-induced fluorescence for detection. This same rabbit antiserum was used on immunoblot analysis. Three bands were observed for material from an infected sheep but none in preparations from brain material from normal sheep. Capillary electrophoresis can be used to show immunocomplex formation when PrP^sc is present in sheep brain.     

Vortex pinning in polycrystalline Eu1.5Ce0.5Sr2Cu2NbO10 from rotational magnetic measurements

Rotational magnetization-vector measurements were carried out on a superconducting polycrystalline disk of EuCSCNO. The results at 4.2 K and low fields resemble recent results for YBa₂Cu₃O_7−δ (YBCO) and Ba_0.57K_0.43BiO₃ (BKBO) in revealing a broad distribution in the strength of the vortex pinning torques. This resemblance extends to higher fields, where it was found that the average pinning torque per vortex (τ_p), which is directly related to the critical current density, decreases steadily with increasing field in a manner consistent with vortex bundling. Quantitatively, however, the values of τ_p for EuCSCNO are smaller by an order of magnitude than those for YBCO but are only moderately smaller than those for BKBO. This comparison supports the notion that the vortex pinning may derive in part from deviations from oxygen stoichiometry, which are normally present in YBCO but are essentially absent in EuCSCNO and BKBO. Moreover, as in YBCO and BKBO, the τ_p in EuCSCNO at fixed field is found to diminish rapidly as the temperature rises towards T_c.     

A possible replacement of single crystal by melt-textured material in the study of YBa2Cu3O7−y

Improved superconducting properties were observed in melt-textured YBa₂Cu₃O_7-y ceramic material. The inductive current density has a small field dependence up to 5.5 T over a wide temperature range. The field and temperature dependences of the magnetic properties are similar to the behavior found in single crystals. Values of the intragrain critical current density in melt-texture samples have the same order of magnitude as in single crystals. The reduced porosity and improved grain alignment help to probe intrinsic physical properties that depend on crystallographic orientation. Thus experiments similar to those involving single crystals are possible. The modified Bean critical state model applied to single crystals can also be used in these melt-textured samples. Thus, it is possible to use melt-textured samples in some basic research which originally required the use of single crystals.     

SYNTHESIS AND SPECTROSCOPIC DIFFERENTIATION OF 2- AND 4-ALKOXYTHIOTETRONIC ACIDS

O-Alkylation of thiotetronic acids gives a mixture of 2- and 4-position enol ether products. Comparison of the physical data revealed that UV spectroscopy was the most reliable method of distinguishing between these related ethers. We have determined that 4-position ethers have a distinct absorption between 235-240 nm, while 2-position ethers have two absorbance peaks, one between 205-220 nm and the other between 305-310 nm. This report describes the synthesis and unambiguous characterization of 2- and 4-methoxy-3,5-dimethylthiotetronic acids. The UV absorption properties of several other pairs of thiotetronic acid ethers confirm that these differences are general features that provide a simple method for distinguishing between 2- and 4-substituted isomers.