Buchbesprechungen

Ohne Zusammenfassung     

Darstellung und Untersuchung von Aminoschwefeltrifluoriden sowie eines Hydrolyseprodukts, 1-(Fluorooxothio)-2,5-dihydropyrrol

Synthesis and Investigation of Aminosulphur Trifluorides and of a Hydrolysis Product 1-(Fluorooxothio)-2,5-dihydropyrrole The reaction of previously unknown (trimethylsilyl)amines with sulphur tetrafluoride gives some new aminosulphurtrifluorides. Experiments to cleaver 1-(Trifluorothio)-2,5-dihydropyrrole and 1-(trifluorothio)pyrrolidin into butadiene and ethylene respectively and NSF₃ by way of a chelotrope cycloelimination were unsuccessful. ¹H-NMR and ¹⁹F-NMR spectra revealed the nitrogen in the aminosulphur trifluorides must be regarded sp³ hybridized rather than sp².     

The kinetics of pyrolysis of barrelene[1]: A concerted process on the C8H8 energy surface

The static vessel pyrolysis of bicyclo[2.2.2]octa-2,5,7-triene (barrelene) has been studied between 483 and 523 K. The products were acetylene and benzene (in equal quantities) with no other detectable C₈H₈ isomer (down to less than 1% of total). The time dependence fitted first-order kinetics, and the data are consistent with a homogeneous unimolecular reaction close to, if not at, its high-pressure limit at 0.25 torr. The rate constant was fitted to the Arrhenius equation These Arrhenius parameters are shown to imply a concerted single-step process. Alternative mechanisms are discussed and a comparison is made with the retro-Diels—Alder reactions of other bicyclo[2.2.2]octa-olefin systems.     

Utilisation de l'antieatalyse dans la chimie analytique

Sans résumé     

On Hall voltage and change of conductivity in transverse magnetic fields of pressed PbO2 powder

The electrical conductivity of a conducting powder is influenced by the properties of the grain surface as well as the grain core. By appropriate variation of pressure and electric frequency, the two contributions can be separated, as long as the grains have shapes nearly like spheres. From experimental data on pressed powders one can thus obtain information concerning carrier density and mobility of bulk material. Results for PbO₂ obtained in this way agree well with the properties of bulk PbO₂ samples reported in the literature.     

Force spectroscopy of single multidomain biopolymers: A master equation approach

Experiments using atomic force microscopy for unfolding single multidomain biopolymers cover a broad range of time scales from equilibrium to non-equilibrium. A master equation approach allows to identify and treat coherently three dynamical regimes for increasing linear ramp velocity: i) an equilibrium regime, ii) a transient regime where refolding events still occur, and iii) a saw-tooth regime without any refolding events. For each regime, analytical approximations are derived and compared to numerically investigated examples. We analyze in the framework of this model also a periodic experimental protocol instead of a linear ramp. In this case, a major simplification arises if the dynamics can be restricted to an effectively two-dimensional subspace. For transitions with an intermediate meta-stable state, like Immunoglobulin27, a refined model allows to extract previously unknown molecular parameters related to this meta-stable state.     

Pomeron vertices in perturbative QCD in diffractive scattering

We analyze the momentum space triple pomeron vertex in perturbative QCD. In addition to the standard form of this vertex which is used in the context of total cross sections at high energies and in the QCD reggeon field theory, there exists an alternative form which has to be used in the study of high-mass diffraction. We review and analyze the relation between these two versions. We discuss some implications for the BK equation. In the second part of our paper we extend this analysis to the pomeron-odderon-odderon vertex.Received: 11 January 2005, Revised: 24 January 2005, Published online: 3 March 2005     

Optical characterization of ultrasmall Si nanoparticles prepared through electrochemical dispersion of bulk Si

Studying the properties and stability of silicon nanoparticles (Si-np) in aqueous environments may lead to novel applications in biological systems. In this work, we use absorption and photoluminescence (PL) spectroscopy to characterize ultrasmall Si-np prepared through anodic etching and ultrasonic fractionation of a crystalline Si wafer. Their behavior is studied over time in 2-propanol and during treatments with water, NaOH, HCl, and H(2)O(2). The observed population is divided into two types of material: bright species consisting of well-etched Si-np, approximately 1 nm in diameter, and dark species derived from partially etched or aggregated Si structures. The dark material is seen by its scattering in the 2-propanol and water solutions and is largely removed via precipitation with the NaOH or HCl treatment. The bright material includes three distinct species with their respective emissions in the UV-B, UV-A, and hard-blue regions of the spectrum. The hard-blue PL is shown to have a simple pH dependence with a pK(a) approximately 3, providing an important insight into its chemical origin and signaling for possible application of Si-np as environmental probes. Our results offer some potential for tailoring the PL properties of ultrasmall Si-np through control of their surface chemistry.