Spectroscopic investigation of the ionization kinetics in XeCl laser discharges by Xe* density measurements

Time and spatially resolved absorption measurements of Xe^* particle number densities performed at an X-ray preionized self-sustained XeCl^*-laser discharge were used to investigate the reaction kinetics of such discharges and to test the validity of the commonly-made assumption that they are fit well by spatially homogeneous numerical models. It turned out that the Xe^* density distribution over the discharge cross section remains homogeneous for less than 100 ns only. Comparing the experimental results of the homogeneous discharge phase with zero-dimensional model calculations, we conclude that induced emission modeled using two excited xenon levels must be taken into account for the quantitative interpretation of the absorption measurements. For the interpretation of the Xe 6s-6p absorption measurements even a multilevel model will be necessary. Further we conclude from the relative courses and the absolute values of the Xe^* particle number densities that realistic HCl kinetics should contain three vibrationally excited levels and stepwise excitation processes as proposed by Dem'yanov et al. [8].     

1,4-Phenylen-bis-diphenylderivate der Elemente der 5. Hauptgruppe des Periodensystems

Zusammenfassung Die Darstellung sämtlicher am mittleren Benzolkern p-substitutierten Verbindungen (C₆H₅)₂ MC₆H₄ M(C₆H₅)₂ mitM=N, P, As, Sb und Bi wird beschrieben. Für die bereits bekannte Stickstoff-bzw. Arsen-Verbindung konnte ein neuer Darstellungs-weg mit guten Ausbeuten gefunden werden, während die Antimon-und Wismutverbindung erstmals beschrieben werden. Durch Dipolmomentmessungen, UV- und IR-Aufnahmen ist ein Vergleich mit den einfachen Triphenylderivaten der genannten Elemente möglich.

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The compounds p-(C₆H₅)₂ MC₆H₄ M(C₆H₅)₂,M=N, P, As, Sb, and Bi, were prepared. New methods for the preparation of the N and As compound with good yields were found. The Sb and Bi compound were synthesized for the first time. Dipole moments, IR- and UV-spectra of these compounds were compared with those of the triphenyl derivates.

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Herrn Prof. Dr.F. Wessely zum 70. Geburtstag gewidmet.     

Luteone,a twenty three carbon terpenoid from the dorid nudi branch Cadlina luteomarginata

The structure of luteone ($\text{1}$), a twenty three carbon terpenoid, has been solved by performing a single crystal x-ray analysis on a 3,4-dinitrophenylhydrazone derivative.     

Determination and confirmation of malachite green and leucomalachite green residues in salmon using liquid chromatography/mass spectrometry with no-discharge atmospheric pressure chemical ionization

A liquid chromatography/mass spectrometry (LC/MS) method was developed to quantitate and confirm residues of leucomalachite green (LMG) in salmon tissue after their conversion to chromic malachite green (MG) in the extraction process. The method uses no-discharge atmospheric pressure chemical ionization (APCI) in conjunction with an ion-trap instrument to generate product-ion spectra. In the sample preparation procedure, salmon tissue is extracted with acetonitrile/buffer, the LMG residue is partitioned into methylene chloride, the LMG is converted to MG using an organic oxidizing agent, and the MG is isolated on alumina/propylsulfonic acid solid-phase extraction cartridges. The method was validated by fortifying salmon with different levels of LMG, and then detecting the residue as MG The LC/MS conditions, including a comparison of electrospray and no-discharge APCI, were evaluated and optimized. MG was not confirmed in any of the control tissue extracts, and all fortified samples analyzed during validation met the confirmation criteria as described. In addition to providing confirmatory data, this method can provide an alternative method for quantitation of MG in salmon. The recoveries of LMG measured as MG by this LC/MS method, at fortification levels of 1-10 ng/g were very high (86-109%), with low relative standard deviation(RSD) values (6.4-13%). The results agreed very closely with those obtained for the same extracts using an LCNIS procedure, indicating that matrix suppression was not an issue. The presence of LMG in salmon tissue samples fortified at 0.25 ng/g was confirmed by this method, with an average recovery of 70.1% and an RSD of 12.0%. Sample extracts from fish exposed to MG were also analyzed.     

Evolutionary rate variation and RNA secondary structure prediction

Predicting RNA secondary structure using evolutionary history can be carried out by using an alignment of related RNA sequences with conserved structure. Accurately determining evolutionary substitution rates for base pairs and single stranded nucleotides is a concern for methods based on this type of approach. Determining these rates can be hard to do reliably without a large and accurate initial alignment, which ideally also has structural annotation. Hence, one must often apply rates extracted from other RNA families with trusted alignments and structures. Here, we investigate this problem by applying rates derived from tRNA and rRNA to the prediction of the much more rapidly evolving 5'-region of HIV-1. We find that the HIV-1 prediction is in agreement with experimental data, even though the relative evolutionary rate between A and G is significantly increased, both in stem and loop regions. In addition we obtained an alignment of the 5' HIV-1 region that is more consistent with the structure than that currently in the database. We added randomized noise to the original values of the rates to investigate the stability of predictions to rate matrix deviations. We find that changes within a fairly large range still produce reliable predictions and conclude that using rates from a limited set of RNA sequences is valid over a broader range of sequences.     

X-ray structure and variable temperature NMR spectra of [meso-triarylcorrolato]copper(III)

The diamagnetic square planar d(8) complexes [meso-arylcorrolato]copper(III) become paramagnetic upon warming, indicative of the equilibrium between the [corrolato]copper(III) and the [corrolato](+)* copper(II) forms of the complex. [meso-Triphenylcorrolato]copper(III) was structurally characterized and found to be saddled.     

Reactions of Molecules with Two Equivalent Functional Groups. 5. Anomalous Reactivity of 1,10-Cyclooctadecanedione. Crystal and Molecular Structures of cis,cis-1,10-Diphenyl-1,10-cyclooctadiene and the Stereoisomers of 1,10-Diphenyl-1,10-cyclooctadecanediol(1)

The reaction of the title diketone (3) with phenyl Grignard produces (with rate constant k(1)) the conjugate base (6-M) of 10-hydroxy-10-phenylcyclooctadecanone (6), which is subsequently converted (with rate constant k(2)) to the conjugate base of the title diol, as a mixture of the cis (7, 55%) and trans (8, 45%) isomers. The ratio k(2)/k(1), 2.2 +/- 0.4, indicates that the carbonyl group in 6-M is 4.4 times as reactive as each carbonyl in 3. Competition experiments further demonstrate that the relative rates (per carbonyl) for addition of phenylmagnesium bromide to 3, 10-methylenecyclooctadecanone (11), and cyclopentadecanone (12) are 1.0:0.60:1.92. Possible reasons for this order of reactivity are discussed. Diols 7 and 8 undergo facile double dehydration to form the title diene 13, which is predicted by molecular mechanics calculations to be the most stable of the four possible symmetrical diene isomers. The structures of 7, 8, and 13 were secured by single-crystal X-ray studies.