Nachweis und Bestimmung der Halogene

Ohne Zusammenfassung     

Reduktionsreaktionen mit Caleiumhvdrid

Ohne Zusammenfassung     

Improved accuracy in the determination of field-flow fractionation elution volumes.

Conventional operation of field-flow fractionation (FFF) systems involves carrying out the analysis at a constant flow of carrier; the flow is temporarily interrupted after injection of a sample in order to permit its equilibration under the applied field. Retention is calculated as the ratio of elution times for a non-retained species and the sample of interest, respectively. Such time-based retentions are only valid if the flow-rate is precisely known at all times during the run. The peristaltic pumps often used with FFF equipment are shown to have an output which varies unpredictably in time. Furthermore, initiation of flow after relaxation is shown to result in significant periods of transient behaviour while the system adjusts to the operating pressure. These and other variations in flow-rate can be eliminated as sources of error by basing the retention measurement on effluent weight, rather than on time. For this purpose, an electronic balance is interfaced with the system's computer, so that detector response/effluent weight data pairs are continuously monitored during the course of the FFF analysis.     

Divergent synthesis of arylated pyridin-2(1H)-one derivatives via metal-catalysed cross-coupling processes

1,5-Di(hetero)arylated-pyridin-2(1H)-one derivatives have been readily obtained in good yields starting from 2-fluoro-5-pyridylboronic acid. The sequence comprises three steps: (i) palladium-catalysed Suzuki-Miyaura reaction; (ii) base-catalysed hydrolysis; (iii) copper-catalysed C-N coupling. X-ray crystal structures are reported for selected pyridin-2(1H)-one derivatives. These compounds are of interest as new scaffolds for drug discovery.     

Certification of total arsenic in blood and urine standard reference materials by radiochemical neutron activation analysis and inductively coupled plasma-mass spectrometry

Radiochemical neutron activation analysis (RNAA) was used to measure arsenic at four levels in standard reference material (SRM) 955c Toxic Elements in Caprine Blood and at two levels in SRM 2668 Toxic Elements in Frozen Human Urine for the purpose of providing mass concentration values for certification. Samples were freeze-dried prior to analysis followed by neutron irradiation for 3 h at a fluence rate of 1 × 10¹⁴ cm^?2 s^?1. After sample dissolution in perchloric and nitric acids, arsenic was separated from the matrix either by retention on hydrated manganese dioxide (urine) or by extraction into zinc diethyldithiocarbamate in chloroform (blood). ⁷⁶As was quantified by gamma-ray spectroscopy. Differences in chemical yield and counting geometry between samples and standards were monitored by measuring the count rate of a ⁷⁷As tracer added before sample dissolution. RNAA results were combined with inductively coupled plasma-mass spectrometry values from National Institute of Standards and Technology and collaborating laboratories to provide certified values of 10.81 ± 0.54 and 213.1 ± 0.73 μg/L for SRM 2668 Levels I and II, and certified values of 21.66 ± 0.73, 52.7 ± 1.1, and 78.8 ± 4.9 μg/L for SRM 955c Levels II–IV, respectively. Because of discrepancies between values obtained by different methods for SRM 955c Level I, an information value of <5 μg/L was assigned for this material.     

A high-throughput monoamine oxidase inhibition assay using liquid chromatography with tandem mass spectrometry

A highly efficient method utilizing liquid chromatography with tandem mass spectrometry (LC/MS/MS) was developed and employed for high-throughput screening of compounds for monoamine oxidase (MAO) inhibition. The method used kynuramine as a common substrate for both MAO-A and MAO-B in incubations, and the 4-hydroxyquinoline (4-HQ) resulting from deamination of kynuramine followed by intramolecular condensation was analyzed using LC/MS/MS; formation of 4-HQ was used as the marker of MAO activity to evaluate the effects of test compounds. Isocratic liquid chromatography was applied to reduce the run time to 2 min. Because of the high specificity and sensitivity of detection of 4-HQ by LC/MS/MS, this method was able to use MAO enzymes at very low concentrations and to perform short incubations; as a result, consumable cost was minimized, and sample preparations were completely avoided. The inhibition data are highly reproducible, and the IC(50) values determined by the method are in good agreement with literature values. The results suggest that this method is very robust and can be used as a generic approach to screen for MAO inhibitors in drug discovery.     

Chromatographic and fluorometric study of interactions between thiophilic and hydrophobic ligands and tryptophan peptide homologues

The interactions of tryptophan and its peptide homologues with thiophilic ligands were studied in terms of their chromatographic retention and steady-state fluorescence under various conditions, and compared with non-polar structures typically regarded as pure hydrophobic ligands. The experimental results show that both non-polar and polar interactions are involved in what has been termed "thiophilic adsorption chromatography".