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21.
22.
R. Henkelmann D. C. Aumann und H. -J. Born 《Fresenius' Journal of Analytical Chemistry》1968,233(1):1-14
Summary Oxygen can be determined by the nuclear reaction 16O (n, p) 16N initiated by fast reactor neutrons. The automatic irradiation and counting system which is used in the Munich research reactor for non-destructive oxygen determination is described. The activation by thermal neutrons is suppressed by the installation of a cadmium shield around the pneumatic tube at the irradiation position. Oxygen has been determined in the presence of many elements to find out which elements disturb the oxygen activation analysis.Zusammenfassung Sauerstoff läßt sich aktivierungsanalytisch mit schnellen Reaktorneutronen über die Kernreaktion 16O (n, p) 16N bestimmen. Die automatische Bestrahlungs- und Meßanlage, die die Durchführung solcher zerstörungsfreier Sauerstoffanalysen am Forschungsreaktor München erlaubt, wird beschrieben. Die Aktivierung durch thermische Neutronen wurde durch Einbau eines Cadmiumschildes am Bestrahlungsort unterdrückt. Sauerstoffanalysen wurden in Gegenwart zahlreicher Matrixelemente durchgeführt, um zu ermitteln, welche Elemente die aktivierungsanalytische Sauerstoffbestimmung mit schnellen Reaktorneutronen erschweren oder unmöglich machen.Wir danken der Betriebsleitung und der Bestrahlungsgruppe des FRM für deren verständnisvolles Eingehen auf unsere Wünsche, Herrn Dr. Köhler für seine wertvollen Hinweise beim Aufbau der schnellen Rohrpost und Herrn E. Pfeffermann für seine Mithilfe bei einem Teil der Messungen. 相似文献
23.
24.
Rudolf O. Duthaler Peter Herold Susanne Wyler-Helfer Martin Riediker 《Helvetica chimica acta》1990,73(3):659-673
Chloro(cyclopentadienyl)bis(1,2:5,6-di-O-isopropylidene-α-D -glucofuranos-3-O-yl)titanium ( 1 ) is used for the transmetallation of Li-enolates obtained from propionyl derivatives. While such Ti-enolates of ketones and hydrazones appear to be unreactive, the (E)enolate 13 of 2,6-dimethylphenyl propionate ( 11 ) adds to the re-side of aldehydes, affording various syn-aldols 14 with high dia- and enantioselectivity (92–97% ds, 91–97% ee, cf. Scheme 2 and Table 1). Racemic syn-aldols (±)- 14 are obtained analogously from the achiral bis(2-propyloxy)-Ti-enolate 15 (Scheme 2 and Table 2). In contrast to the unstable Li-enolate 10 , the Ti-enolates 13 and 15 isomerize at ?30°, presumably to the thermodynamically more stable (Z)-enolates (Scheme 4), While the diastereoselectivity of the achiral enolate 15 is lost upon this equilibration, the chiral (Z)-enolate 27 quite unexpectedly affords anti-aldols 12 of high optical purity (94–98% ec) and, in most cases, with acceptable-to-good diastereoselectivity (82–90% ds). Notable exceptions are branched unsaturated and aromatic aldehydes which form a greater proportion of synepimers of moderate optical purity (Scheme 5 and Table 3). Consistent with these findings, re-facial-and ami -selective aldol-addition is also exhibited by the (Z)-configurated Ti-enolate 22 of N-propionyl-oxazolidi-none 19 (Scheme 3). 相似文献
25.
26.
Trace analysis of rapamycin in human blood by micellar electrokinetic chromatography 总被引:1,自引:0,他引:1
A capillary electrophoretic method with UV detection at 278 nm has been developed for analysis of the immunosuppressant rapamycin (sirolimus) in human blood at low microgram per liter levels. Separation has been achieved in an acidic carrier electrolyte containing sodium dodecylsulfate and 30% (v/v) acetonitrile. For sample clean-up and preconcentration, an off-line solid-phase extraction step using a silica-based reversed-phase material and an on-capillary focussing technique were employed. The latter allows the injection of increased sample volumes without excessive band broadening. Although this new method is less sensitive than existing liquid chromatographic procedures combined with mass spectrometry, it is fully suited to routine analysis of rapamycin in blood from patients treated with this drug. Last but not least the low costs make it an attractive alternative to established methods. 相似文献
27.
28.
The enzymatic elongation of acyl-CoA esters by malonyl-CoA, respectively de novo synthesis of fatty acids from malonyl-CoA by liver microsomes and non particulate fraction of α-tocopherol deficient rats is diminished versus controls. However, liver microsomes of vitamin E deficient rats synthesize more eicosatetraenic acid from γ-linolenic acid and more γ-linolenic acid from linolic acid than do those of tocopherol supplemented animals. It has often been shown that the liver phosphatides of tocopherol deficient rats contain more arachidonic acid than those of controls, a fact which can be explained now by increased activity of the enzymes involved in the biosynthesis of arachidonic acid. Certain polyenic fatty acids are more rapidly synthesized in the absence of naturally occuring antioxidants. Some enzymes of the respiratory chain have also been examined. No vitamin E deficiency effect has been found on enzymes such as gluconate-6-P-dehydrogenase, isocitrate-dehydrogenase, malate-dehydrogenase and lactate dehydrogenase contained in the non particulate fraction. Sonicated mitochondria of tocopherol deficient rats show a greater activity towards cytochrome, oxydase and β-hydroxy-acetyl-CoA-dehydrogenase than controls, possibly due to ultrastractural alteration of this particle. 相似文献
29.
(±)-Muscone (5) has been synthesized from methyl 13-(chloroformyl)tridecanoate (6) in nine steps in an overall yield of 24%. The key steps involve an efficient transformation of the readily accessible 14-hydroxy-15-methyl-15-hexadecenoic acid (9) into the tetradecanolide 1 and a subsequent Ireland-Claisen rearrangement of its triethylsilyl enolate 2 to a 8:1-mixture of the stereoisomeric 15-membered carbocycles 4 and 10 (Scheme 4). 相似文献
30.
Boisguerin P Leben R Ay B Radziwill G Moelling K Dong L Volkmer-Engert R 《Chemistry & biology》2004,11(4):449-459
SPOT synthesis permits parallel synthesis and screening of thousands of cellulose membrane-bound peptides to study protein-protein interactions in a proteomic context. Recognition of C-terminal residues is one of the most common binding features of PDZ domains. Unfortunately, most solid support-bound peptide libraries lack a free C terminus due to C-terminal fixation on the solid support. To overcome this restriction, we developed a robust methodology based on our previous strategy for generating peptides with authentic C termini. To validate this improved method, we screened a human peptide library of 6223 C termini with the syntrophin PDZ domain. Furthermore, using the same library, new peptide ligands derived from membrane proteins and receptors were found for the ERBIN PDZ domain. Finally, we identified the protein kinase breakpoint cluster region, which is known as a negative regulator of cell proliferation and oncogenic transformation, as an ERBIN ligand. 相似文献