Equilibrium Formation of Stable All‐Silicon Versions of 1,3‐Cyclobutanediyl

Main group analogues of cyclobutane‐1,3‐diyls are fascinating due to their unique reactivity and electronic properties. So far only heteronuclear examples have been isolated. Here we report the isolation and characterization of all‐silicon 1,3‐cyclobutanediyls as stable closed‐shell singlet species from the reversible reactions of cyclotrisilene c‐Si₃Tip₄ (Tip=2,4,6‐triisopropylphenyl) with the N‐heterocyclic silylenes c‐[(CR₂CH₂)(NtBu)₂]Si: (R=H or methyl) with saturated backbones. At elevated temperatures, tetrasilacyclobutenes are obtained from these equilibrium mixtures. The corresponding reaction with the unsaturated N‐heterocyclic silylene c‐(CH)₂(NtBu)₂Si: proceeds directly to the corresponding tetrasilacyclobutene without detection of the assumed 1,3‐cyclobutanediyl intermediate.     

Comparison of electron spin resonance probe and dielectric relaxation in physically and chemically crosslinked polymers

Dielectric relaxation spectroscopy in the frequency range from 10⁻² Hz to 10⁶ Hz and electron spin resonance (ESR) experiments are employed to study the dynamics in chemically and physically crosslinked networks. As examples for physically crosslinked networks ortho- and para-cresol novolacs were investigated. Dielectrically these materials show low-temperature β- and high-temperature α-relaxation. Both relaxation regions differ for both types of novolacs. This is also reflected by the ESR measurements and is discussed in terms of different hydrogen bonds found to be stronger in para-cresol novolac. For the chemically crosslinked poly(triallyl isocyanurate) only a β-peak is found by the dielectric measurements. Also in the ESR experiment the slow motion regime is characterized up to high temperatures. This means that the segmental motion is strongly suppressed by chemical crosslinking. Nevertheless the obtained change in the formal T_50G value can be used to characterize the glass transition in highly crosslinked systems by the ESR method.     

Radial flow velocity profiles of a yield stress fluid between smooth parallel disks

In rock grouting, idealized 2D-radial laminar flow of yield stress fluids (YSF) is a fundamental flow configuration that is used for cement grout spread estimation. A limited amount of works have presented analytical and numerical solutions on the radial velocity profiles between parallel disks. However, to the best of our knowledge, there has been no experimental work that has presented measured velocity profiles for this geometry. In this paper, we present velocity profiles of Carbopol (a simple YSF), measured by pulsed ultrasound velocimetry within a radial flow model. We describe the design of the physical model and then present the measured velocity profiles while highlighting the plug-flow region and slip effects observed for three different apertures and volumetric flow rates. Although the measured velocity profiles exhibited wall slip, there was a reasonably good agreement with the analytical solution. We then discuss the major implications of our work on radial flow.

     

A polarographic study of propene-maleic anhydride copolymers

The polarographic behaviour of hydrolyzed propene-maleic anhydride copolymers in the interval pH 2.0–11.0 has been investigated by differential pulse polarography in aqueous lithium chloride solution at 25°C. In dependence on the pH-value, one, two or three signals, belonging to the acid groups in the copolymer, appear in the polarograms. Three apparent polarographic acid constants have been determined graphically from the changes in the half-wave potential of the separate peaks in correlation with pH.     

Metabolic profiling of rodent biological fluids via 1H NMR spectroscopy using a 1 mm microlitre probe

The application of a 1 mm TXI (1H/13C/15N) microlitre NMR probe with z-gradient for metabolic profiling of biofluids is described. The probe was used to provide spectral profiles for rat blood plasma using only approximately 2 microl of fluid with a range of solvent suppression techniques. Using a similar amount of fluid, spectra were obtained from rat and mouse cerebrospinal fluid, demonstrating that the probe could be used to profile rodents metabolically via biofluids previously inaccessible to NMR analysis without the need for termination.     

Generation of 100 μJ pulses at 82.8 nm by frequency tripling of sub-picosecond KrF laser radiation

. Investigations of the efficient generation of powerful coherent radiation at 82.8 nm by frequency tripling of short-pulse KrF laser radiation are presented. Argon gas is selected as nonlinear medium due to the resonantly enhanced 3rd-order susceptibility χ⁽³⁾(-3ω,ω,ω,ω). Pulse energies of 100 μJ at 82.8 nm have been measured for a pump pulse energy of 14 mJ. An upscaling to more than 500 μJ is expected with available more powerful pump lasers. Features of this XUV source and possible applications are discussed. Received: 26 July 2002 / Published online: 15 November 2002 RID="*" ID="*"Corresponding author. Fax: +49-511/7622211, E-mail: reinhardt@iqo.uni-hannover.de     

Superior laryngeal nerve paresis and paralysis

Superior laryngeal nerve paresis and paralysis are relatively common but often difficult to diagnose with certainty. They are most commonly caused by viral infections, though other etiologies must be considered. A thorough history and physical examination, including strobovideolaryngoscopy and laryngeal electromyography, are needed for definitive diagnosis. It is essential to establish the diagnosis accurately to differentiate an apparent superior laryngeal nerve paresis from other conditions, such as myasthenia gravis. Laryngeal electromyography is used to confirm clinical impressions, as a guide for therapy, and as one measure of recovery. In our experience, accurate and early diagnosis assure the best phonatory outcome by directing therapy that will prevent or eliminate compensatory vocal abuses, which may themselves lead to even more serious vocal injury.