A tertiary hydroxy group α to a carboxyl moiety comprises a key structural motif in many bioactive substances. With the herein presented metal‐free rearrangement of imides triggered by hypervalent λ3‐iodane, an easy and selective way to gain access to such a compound class, namely α,α‐disubstituted‐α‐hydroxy carboxylamides, was established. Their additional methylene bromide side chain constitutes a useful handle for rapid diversification, as demonstrated by a series of further functionalizations. Moreover, the in situ formation of an iodine(III) species under the reaction conditions was proven. Our findings clearly corroborate that hypervalent λ3‐benziodoxolones are involved in these organocatalytic reactions. 相似文献
Zusammenfassung. Mit Hilfe der projektiven Geometrie werden neuartige Summationsformeln hergeleitet, die die Tschebyscheff-Polynome und modifizierte Polynome enthalten; z. B. gilt für alle :
Daraus ergeben sich wiederum interessante Summationsformeln für die Hyperbelfunktionen; es gilt z. B. für positive reelle
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Eingegangen am 28.02.96, revidierte Fassung am 25.08.97 / Angenommen am 09.10.97 相似文献
The association constant K of mono-acetato complex of Tb3+ has been determined at normal p and T conditions by measurement of its luminescence lifetime in aqueous solution containing increasing concentrations of acetate. Two experimental arrangements used for the measurement are described. 相似文献
A capillary electrophoretic (CE) method was developed for the separation of diastereoisomers of a new human immunodeficiency virus (HIV) protease inhibitor TMC114. In total 16 isomers of this drug have been synthesized (eight pairs of enantiomers). We succeeded in the separation of the eight diastereoisomers, but no enantiomers could be separated. Because of the high similarity and water-insolubility of these isomers, the separation is a real challenge. Different CE modes were tried out: capillary zone electrophoresis (CZE), nonaqueous capillary electrophoresis (NACE), micellar electrokinetic capillary chromatography (MEKC), and microemulsion electrokinetic capillary chromatography (MEEKC). Only MEEKC offered resolution of these compounds. 相似文献
Sulfur(IV) Compounds as Ligands. II. The Crystal and Molecular Structure of Pentacarbonyl--(sulfur dioxide)chromium The structure of pentacarbonyl(sulfurdioxide)chromium ( 1 ) has been determined from single crystal X-ray data. The compound crystallizes with eight formula units in the rhombic unit cell (space group Pbn21) of the dimensions a = 657.8(2) pm, b = 1245.2(4) pm, c = 2177.4(5) pm (at 180 K). The sulfur dioxide is η1-coplanar coordinated, the Cr? S distance is 219 pm, the shortest bond reported so far between chromium(0) and sulfur. The Cr? C(ax) bond (189 pm) was found only marginally shorter than the Cr? C(eq) bonds (190 pm) providing proof of the high π-acceptor capacity of SO2. 相似文献
The identification of drug targets for pharmaceutical screening can be greatly accelerated by gene databases and expression studies. The identification of leading compounds from growing libraries is realized by high throughput screening platforms. Subsequently, for optimization and validation of identified leading compounds studies of their functionality have to be carried out, and just these functionality tests are a limiting factor. A rigorous preselection of identified compounds by in vitro cellular screening is necessary prior to using the drug candidates for the further time consuming and expensive stage, e.g. in animal models. Our efforts are focused to the parallel development, adaptation and integration of different microelectronic sensors into miniaturized biochips for a multiparametric, functional on-line analysis of living cells in physiologically environments. Parallel and on-line acquisition of data related to different cellular targets is required for advanced stages of drug screening and for economizing animal tests. 相似文献
A new approach has been developed and tested for the urgent analysis of dioxins in samples of air-dust filters originating from catastrophe emissions. The procedure consists of a fast extraction of the sample with microwave solvent extraction (MASE) and acetone as solvent followed by a fast cleanup of the extract with normal phase coupled column liquid chromatography (LC/LC).
The multi-dimensional LC/LC system employs a 50 mm×4.6 mm i.d. column packed with 3 μm silica and a 150 mm×4.6 mm i.d. column packed with 5 μm PYE as the first and second analytical column, respectively. Iso-hexane is used on both columns to perform cleanup and dichloromethane to perform efficient back-flush elution of the compounds from the second column. The obtained polarity-based separation in the first dimension and molecular-structure based separation in the second dimension provides a fast and powerful cleanup.
Validation was done by analysing samples of homemade RIVM air-dust with aged residues (n=8, spiking level about 15 pg mg−1 per compound) of dioxins/furans and samples of reference Urban Dust SRM 1649a (n=4) with both the new approach and the existing conventional procedure and were instrumentally analyzed with capillary gas chromatography and high resolution mass spectrometric detection (GC/HRMS).
In comparison to the existing conventional procedure, the new approach reduces sample processing from several days to several hours per sample.
As regards the aged-residue air-dust samples, the new method shows a good accuracy, precision and high selectivity providing a performance in good agreement with the existing procedure. In SRM air-dust, the concentration of a few compounds obtained by the new method was below (10–50%) the certified value. 相似文献
Modern drug development requires technologies that allow rapid translation from the preclinical to the clinical stage. It is obvious that non-invasive imaging modalities such as magnetic resonance imaging (MRI) will play a central role in this regard. This article reviews the use of structural and functional MRI readouts for characterization of central nervous system (CNS) disorders and evaluation of the efficacy of potential CNS drugs. Examples comprise dementia of Alzheimer's type, cerebral ischemia, and neuroinflammation covering both clinical and preclinical aspects. In these examples MRI has been used to obtain relevant structural information on brain atrophy, on the location and extent of ischemic brain areas, and on the number and distribution of demyelinated plaques. These structural data are complemented by readouts assessing the functional consequences associated with the pathomorphological changes. In the last decade, MRI has evolved into a standard tool for the development of CNS drugs. With regard to target-specific/molecular imaging applications MRI is limited by its inherently low sensitivity; complementary imaging modalities utilizing optical and radionuclear reporter systems will thus be required. 相似文献