The change of the superstructure of semicrystalline polymers during deformation: results from small-angle scattering with synchrotron radiation

The change of the superstructure of different polyethylenes during uniaxial deformation is investigated. The method used is small-angle scattering with synchrotron radiation. For branched polyethylene (Lupolen 1840D) the whole deformation range is analyzed. Beginning with superstructure of the lamellar cluster type, the superstructure partly disappears on a time scale of a few minutes and the fibrillar structure is built up. The degree of destruction and rebuilding depends on the drawing temperature. For very high molecular weight polyethylene (GUR) a reversible change of the superstructure at higher deformation ratios and at different temperatures is observed. The superstructure of (ethylene—hexene) copolymers (TIPELIN) at high draw ratios depends on the drawing temperature and is almost independent of the side group content. Interfibrillar microcracks parallel to the draw direction are produced in samples with a low side group content for draw ratios λ ≥ 1.5.     

Simulated cosmic strings in a “big bang” in superfluid3He at 100 μK

During studies of the impact of single neutrons on superfluid³He at around 100μK we have measured the thermal energy released in the superfluid following the nuclear reaction, n+³He→p+³H+764keV. However, we find that the measured energy deposited in the quasiparticle system shortly after this reaction is substantially less than what we expect. We believe that this energy deficit represents that energy which has gone into the creation of vortices, in analogy to the creation of cosmic strings in the early universe via the Kibble mechanism. Furthermore, from the magnitude of the deficit, we can infer the vortex density which compares favorably with that predicted in Zurek’s scenairo.     

Some Characterizations of Ergodic Probability Measures

Let P be a Markov kernel defined on a measurable space (X, ??). A P-ergodic probability is an extreme point of the family of all P-invariant probability measures on ??. Several characterizations of P-ergodic probabilities are given. In particular, for the special case of a topological space X both P-ergodic Baire probabilities and P-ergodic Borel probabilities with additional regularity properties are characterized.     

Intramolecular hemiacetals. The acid-base-catalyzed ring-chain interconversion of 2-substituted 2-hydroxy-4,4-dimethylmorpholinium cations in aqueous solution.

The ring-chain tautomerism in aqueous solution of some aryl-substituted morpholinium salts (bromides), has been studied and equilibrium constants are reported. In the crystals the substrates exist entirely in their cyclic forms as hemiacetals, but in aqueous solution NMR measurements reveal that an equilibrium is established between the cyclic (hemiacetal) and the noncyclic (ketone) form, the degree of ring-opening being more pronounced with electron-donating aryl substituents at the carbonyl carbon. The kinetics of the ring-chain interconversion in water has been investigated spectrophotometrically by a 'pH jump' stopped-flow technique. General base catalysis is observed with a Br?nsted beta value apparently independent of substituent and equal to 0.60. The Hammett rho values for various base catalysts are close to those for very similar intermolecular reactions involving hemiacetal breakdown, leading to the suggestion of a 'normal' class n mechanism for base catalysis. For acid catalysis, however, a quite different situation is encountered, since no general acid but only (weak) catalysis by the hydronium ion can be detected. We believe this deviation from 'normal' general acid catalysis is caused by an electrostatic interaction, and we suggest that it might result from a change in the usual class e mechanism for general acid catalysis by a situation in which rate-limiting concerted proton transfer is replaced by rate-limiting preprotonation. This is supported by the observed drastic change in Hammett rho value for catalysis by the hydronium ion, compared with the 'normal' case. An interesting case is encountered for the 4-aminophenyl-substituted substrate, in which the amino group becomes protonated in acid solution, thus representing a new substituent. Despite this complication, the various equilibrium and rate constants may also be evaluated experimentally for this substrate.     

Monitoring genomic alterations with a panel of oligonucleotide probes specific for various simple repeat motifs

Germline and somatic instability of the human genome was studied, using synthetic oligonucleotides specific for simple repeat motifs. The following probes were used: (GTG)5, (GACA)4, (GATA)4, (CT)8, (TTAGGG)3, (GT)8, (GAA)6 and (GGAT)4. Each of them is unique with respect to the target regions recognized in the genome. Thus compilation of the various fingerprint data provides a complex map of the genome (and its deviations). While the fingerprints of differentiated somatic tissues never showed any alterations, in tumor tissues (namely gliomas) many changes could be detected. Most of the latter reflect secondary karyological aberrations. In nearly one third of the gliomas, drastically amplified and apparently monomorphic DNA fragments were identified. This marker should make it possible to deal with causal pathogenetic mechanisms as well as novel diagnostic strategies.     

Multiple Wavelength Extinction Technique for Particle Characterization in Dense Particle Clouds

In utilizing the advantages of extinction measurements in micron and especially submicron particle characterization, the properties of a multiple wavelength extinction technique have been the subject of extended theoretical studies. Furthermore, an experimental set-up was designed which provides high flexibility owing to its modular design. The performance of the technique described is demonstrated by a large variety of applications in aerosol and combustion research and in large-scale industrial systems. It was found to be a reliable tool in characterizing dense particulate systems.