Experimental Evidence for the Existence of Neutral P(6): A New Allotrope of Phosphorus

High-energy collisions of Cp*P(6)(+) cations yield neutral P(6) molecules (see reaction), thus providing the first experimental evidence for the existence of this new allotrope of phosphorus.     

Determination of (13)C natural abundance of amino acid enantiomers in soil: methodological considerations and first results

The application of a combined gas chromatography-combustion/isotope ratio mass spectrometry (GC-C/IRMS) method for stable carbon isotope analysis of amino acid enantiomers in soil samples is presented. Triplicate delta(13)C analyses of pentafluoropropionyl (PFP) isopropyl ester derivatives of 27 amino acid enantiomers revealed that discrimination of (13)C during derivatization is different for different amino acid enantiomers and different amounts. Injection of increasing amounts of amino acid derivatives showed that the isotopic signal varied up to 10 per thousand for D-aspartic acid. Correction for the delta(13)C signal of underivatized amino acid enantiomers is possible for all investigated amino acid enantiomers using logarithmic functions. Operating the GC-C/IRMS system in the split-mode (split ratio 1:12) is possible but resulted in a higher isotopic discrimination. The detection limit approached 3 ng for some amino acid enantiomers in the splitless mode, while the lower limit of routine determination exceeded 10 ng injection amount. The upper limit at which accurate stable isotope values were obtained was 200 ng injection amount. Compound-specific delta(13)C analysis of alanine, valine, aspartic and glutamic acid showed that the D-forms were enriched in (13)C relative to the L-forms, suggesting that microbes significantly contributed to the formation of the D-enantiomers in soil.     

Correlating Molar Mass, π-Conjugation,and Optical Properties of Narrowly Distributed Anionic Polythiophenes in Aqueous Solutions

Polythiophene-based conjugated polyelectrolytes (CPE) are attracting increasing attention as sensor or interface materials in chemistry and biology. While cationic polythiophenes are better understood, limited structural information is available on their anionic counterparts. Limited access to well-defined polymers has made the study of structure-property relationships difficult and clear correlations have remained elusive. By combining controlled Kumada catalyst transfer polymerization with a polymer-analog substitution, regioregular and narrowly distributed poly(6-(thiophen-3-yl)hexane-1-sulfonate)s (PTHS) with tailored chain length are prepared. Analysis of their aqueous solution structures by small-angle neutron scattering (SANS) revealed a cylindrical conformation for all polymers tested, with a length close to the contour length of the polymer chains, while the estimated radii remain too small (<1.5 nm) for extensive π-stacking of the chains. The latter is particularly interesting as the longest polymer exhibits a concentration-independent structured absorption typical of crystalline polythiophenes. Increasing the ionic strength of the solution diminishes these features as the Coulomb repulsion between the charged repeat units is shielded, allowing the polymer to adopt a more coiled conformation. The extended π-conjugation, therefore, appears to be a key parameter for these unique optical features, which are not present in the corresponding cationic polythiophenes.     

Photoconductance‐calibrated photoluminescence lifetime imaging of crystalline silicon

We use photoluminescence (PL) measurements by a silicon charge‐coupled device camera to generate high‐resolution lifetime images of multicrystalline silicon wafers. Absolute values of the excess carrier density are determined by calibrating the PL image by means of contactless photoconductance measurements. The photoconductance setup is integrated in the camera‐based PL setup and therefore identical measurement conditions are realised. We demonstrate the validity of this method by comparison with microwave‐detected photoconductance decay measurements. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Nichtlineare Stabilitätsuntersuchungen mit der Methode der Finiten Elemente

Übersicht Ziel der Arbeit ist die exakte und genäherte Bestimmung der kritischen Last von elastischen Systemen mit nichtlinearem Vorbeulverhalten. Grundlage ist die Verschiebungsformulierung der Methode der finiten Elemente in inkrementell/iterativer Darstellung. Im ersten Hauptteil werden begleitende Stabilitätsuntersuchungen bei der exakten Auswertung der nichtlinearen Gleichungen behandelt. Hierzu gehören die Determinantenbeobachtung sowie Eigenwertuntersuchungen für den Lastparameter und die Eigenfrequenz. Im zweiten Hauptteil werden zwei verbesserte Anfangsstabilitätsanalysen zur genäherten Bestimmung der kritischen Last vorgestellt, die auf Reihenlösungen der Gleichgewichts- und Stabilitätsgleichungen basieren. In beiden Teilen bestätigen zahlreiche Beispiele die Brauchbarkeit der behandelten Verfahren.

---

Nonlinear stability analysis in finite element formulation

Summary Exact and approximate solutions for the critical load of elastic structures exhibiting a nonlinear prebuckling response are described. The incremental iterative displacement finite element formulation is used. Two main aspects are covered. First different supplementary procedures evaluating the stability citerion parallel to the nonlinear analysis are investigated. Among these are the function of the determinant, and eigenvalue formulations for the load parameter and the frequency. In the second part two improved initial stability analyses are proposed to determine an approximate solution of the final critical load. They are based on the perturbation method in which the equilibrium and stability equations are expanded in series solutions. In both parts several numerical examples are given.