Transportmechanismen und Ausbeuten beim TAS — Verfahren

In the TAS procedure, substances which can be separated from a sample by thermal increase of the vapour pressure can be transported to the TLC layer in different ways and with varying effectiveness. “Forced Convection” gives the lowest yields, results improve considerably with the so-called carrier gas extraction, and a carrier gas extraction in a stream of helium results in optimal yields. Nipagin^®, Sudan red, Dimethyl yellow, Menadione^® and Diphenyl were used as model substances. An almost quantitative thermoextraction from samples can only be achieved with amounts of less than 20 μg. Following scraping off and elution of the corresponding TLC-zones a photometric assay is carried out for quantitative determination.     

Determination of alkali metals leached from glass ampoules into injection fluids

Direct determination of the alkali metal output of glass ampoules by atomic emission and absorption spectrometry is described. The methods provide suitable alternatives to acidimetric titration for characterizing the hydrolytic resistance of container glasses for pharmaceutical use.     

On the application of ICP-MS techniques for measuring uranium and plutonium: a Nordic inter-laboratory comparison exercise

Inductively coupled plasma mass spectrometry (ICP-MS) techniques are widely used for determination of long-lived radionuclides and their isotopic ratios in the nuclear fields. Uranium (U) and Plutonium (Pu) isotopes have been determined by many researchers with ICP-MS due to its relatively high sensitivity and short measurement time. In this work, an inter-laboratory comparison exercise among the Nordic countries was performed, focusing on the measurement of U and Pu isotopes in certified reference materials by ICP-MS. The performance and characters of different ICP-MS instruments are evaluated and discussed in this paper.     

Analysis of phenolic choline esters from seeds of Arabidopsis thaliana and Brassica napus by capillary liquid chromatography/electrospray‐ tandem mass spectrometry

Total phenolic choline ester fractions prepared from seeds of Arabidopsis thaliana and Brassica napus were analyzed by capillary LC/ESI‐QTOF‐MS and direct infusion ESI‐FTICR‐MS. In addition to the dominating sinapoylcholine, 30 phenolic choline esters could be identified based on accurate mass measurements, interpretation of collision‐induced dissociation (CID) mass spectra, and synthesis of selected representatives. The compounds identified so far include substituted hydroxycinnamoyl‐ and hydroxybenzoylcholines, respective monohexosides as well as oxidative coupling products of phenolic choline esters and monolignols. Phenolic choline esters are well separable by reversed‐phase liquid chromatography and sensitively detectable using electrospray ionization mass spectrometry in positive ion mode. CID mass spectra obtained from molecular ions facilitate the characterization of both the type and substitution pattern of such compounds. Therefore, LC/ESI‐MS/MS represents a valuable tool for comprehensive qualitative and quantitative analysis of this compound class. Copyright © 2008 John Wiley & Sons, Ltd.     

Zur Kenntnis der Rheometrie organischer Gläser

Zusammenfassung Die vorliegende Abhandlung besch?ftigt sich mit der Erforschung der Zusammenh?nge zwischen Flie?eigenschaften und Temperatur. Nach eingehender Diskussion der verschiedenen Flie?kurventypen werden die Flie?kurvendiagramme von 4 Polyvinylazetaten besprochen und der Begriff der Verformungsleistung entwickelt. Die Abh?ngigkeit der Verformungsleistung von der Temperatur kann durch eine ?hnliche Gleichung dargestellt werden, wie sie von Andrade und Sheppard für die Temperaturabh?ngigkeit der Viskosit?t angegeben wurde. Dadurch wird eine allgemeinere Auswertung von Flie?kurvendiagrammen m?glich. Die Verfasser danken dem Direktor der Reichsforschungsanstalt für Kleintierzucht, Herrn Prof. Dr. A. Koch, für sein wohlwollendes und stets f?rderndes Interesse an der Aufdeckung der mitgeteilten Zusammenh?nge. Wir danken der Firma Dr. Alexander Wacker, München, für die überlassung der verschiedenen Polyvinylazetate sowie Herrn Generaldirektor Wilke, Mitteldeutsche Spinnhütte G. m. b. H., Celle, für die Bereitstellung eines Ultrathermostaten. Unser Dank gilt ferner der Deutschen Forschungsgemeinschaft, die ein Konsistometer zur Verfügung stellte.     

A "push-pull" mechanism for heterolytic o-o bond cleavage in hydroperoxo manganese porphyrins

A water-soluble manganese porphyrin, 5,10,15,20-tetrakis-(1,3-dimethylimidazolium-2-yl)porphyrinatomanganese(III) (Mn(III)TDMImP) is shown to react with H(2)O(2) to generate a relatively stable dioxomanganese(V) porphyrin complex (a compound I analog). Stopped-flow kinetic studies revealed Michaelis Menton-type saturation kinetics for H(2)O(2). The visible spectrum of a compound 0 type intermediate, assigned as Mn(III)(OH)(OOH)TDMImP, can be directly observed under saturating H(2)O(2) conditions (Soret band at 428 nm and Q bands at 545 and 578 nm). The rate-determining O-O heterolysis step was found to have a very small activation enthalpy (ΔH(≠) = 4.2 ± 0.2 kcal mol(-1)) and a large, negative activation entropy (ΔS(≠) = -36 ± 1 cal mol(-1) K(-1)). The O-O bond cleavage reaction was pH independent at 8.8 < pH < 10.4 with a first-order rate constant of 66 ± 12 s(-1). These observations indicate that the O-O bond in Mn(III)(OH)(OOH)TDMImP is cleaved via a concerted "push-pull" mechanism. In the transition state, the axial (proximal) (-)OH is partially deprotonated ("push"), while the terminal oxygen in (-)OOH is partially protonated ("pull") as a water molecule is released to the medium. This mechanism is reminiscent of O-O bond cleavage in heme enzymes, such as peroxidases and cytochrome P450, and similar to the fast, reversible O-Br bond breaking and forming reaction mediated by similar manganese porphyrins. The small enthalpy of activation suggests that this O-O bond cleavage could also be made reversible.     

Reactive ion scattering from ice in a molecular dynamics perspective

This is a study into the scattering dynamics of the alkaline ions Cs⁺, K⁺, Na⁺, and Li⁺ from an ice surface, and the process of abstracting water molecules by the scattered ions to form ion–water clusters as a result of the ion–dipole attraction. In a classical molecular dynamics computer simulation a semi-empirical ion–water interaction potential and a modified version of the TIP3P ice model are employed.The thickness of the ice structure at the surface greatly affects the abstraction efficiency. From a thin ice overlayer all alkaline ions exhibit similar scattering probabilities, but Cs⁺ abstracts water molecules most efficiently; its lower speed facilitates a mechanism where the Cs⁺ in its outgoing trajectory pulls water molecules out of the ice structure. From a thick ice structure the scattering probabilities decrease dramatically due to an effective energy transfer to the ice structure. A more grazing angle of incidence reduces the energy transfer and enhances the scattering probabilities for the lighter alkaline ions. The deprived formation of ion–water clusters in the simulations confirms that from thick ice the cluster formation probability is reduced by at least three orders of magnitude.     

Waveguide and diode heterodyne measurements with CO2 laser and assignment of the CW FIR laser emission of OCS

Heterodyne spectra of carbonyl sulfide have been obtained with saturation in a CO₂ waveguide laser and without saturation with a diode laser. The absolute uncertainties of the measured positions lie between 10⁻⁴ and 7 × 10⁻⁶ cm⁻¹. The CW submillimeter laser line of OCS at 378 μm has been assigned to the J = 65 → 64 transition in the 02²0e state of ¹⁶O¹²C³²S, with a pumping through the R(64) line of 02²0e ← 00⁰0, a Δ-Σ transition weakly allowed by the l-type resonance.