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91.
Oxalic acid determinations are made using two modes of electrochemical detection, namely, classical d.c. and differential pulse, after separation by ion-pair, ion exchange high performance liquid chromatography. Peak height ratio plots are constructed and compared for uric acid and oxalic acid mixtures using both electrochemical detection modes. The enhanced selectivity realized by use of the differential pulse electrochemical detection mode is demonstrated. 相似文献
92.
A tethered imine-enamine methodology has been developed for the direct conversion of 1,2,4-triazines into highly substituted pyridines via the inverse electron demand Diels-Alder reaction which avoids the need for a discrete aromatisation step. This TIE methodology has also been applied in one pot reaction cascades involving 1,2,4-triazines and utilising MnO(2)-mediated tandem oxidation processes (TOPs). 相似文献
93.
Yoshim Tokura Richard L. Edelson Francis P. Gasparro 《Photochemistry and photobiology》1993,58(6):822-826
Abstract The effects of cell differentiation and mitogen and phorbol ester stimulation on the formation of 8-methoxypsoralen (8-MOP)-DNA photoadducts in murine T lymphocytes were examined using 3 H-8-MOP. While there were no significant differences in 8-MOP photoadduct formation among BALB/c thymocytes, splenocytes, splenic T cells and MRL/1pr lymph node cells, BALB/c bone marrow cells showed fewer photoadducts than did the lymphocytes. This suggested that proliferating progenitor cells may be resistant to 8-MOP photoadduct formation. Incubation of purified splenic T cells with lectin mitogens for 2 h or with phorbol 12-myristate 13-acetate (PMA) for 2–43 h resulted in reduction of 8-MOP photoadduct formation in the DNA, whereas 64 h cultivation with these agents augmented the photoadduct formation. The reduction of photoadduct formation induced by phytohemagglutinin was restored by the further addition of a protein kinase C (PKC) inhibitor, H-7, to the culture. Thus, it is assumed that the reduction of adduct formation evoked by mitogens and PMA is mediated in part by the activation of PKC in the cells. On the other hand, the augmentation of the adduct formation induced by the longer-period cultures with mitogens and PMA appeared to be caused by down-regulation of PKC. The present study showed that the stimulatory signals in which PKC is presumably involved affect the ability of cells to form 8-MOP-DNA photoadducts. 相似文献
94.
An unprotected 16 residue peptide containing a C-terminal thioester and an N-terminal selenocysteine residue efficiently cyclizes in the presence of thiophenol; subsequent reduction, elimination or alkylation of the selenol yields modified cyclic peptides with alanine, dehydroalanine or a non-natural amino acid at the site of ligation. 相似文献
95.
Substituted carbazoles are readily prepared in good yields by the palladium-catalyzed cross-coupling of alkynes and N-(3-iodophenyl)anilines. This process proceeds by carbopalladation of the alkyne, heteroatom-directed vinylic to aryl palladium migration, and ring closure involving two consecutive C-H activation processes. The process has also been expanded to the synthesis of an indole. [Structure: see text] 相似文献
96.
Carbonyl 2 + 2 photoaddition occurs selectively to the alkene moiety of 3-(4-methyl-3-pentenoxy)pyridine. Photolysis of alkene containing pyridines in acetophenone gives rise to an oxetane which is obtained with extremely high diastereoselectivity as shown by analysis of the major 2 + 2 photoproduct. A second photoproduct, 2,3-dihydroxy-2,3-diphenylbutane, is obtained as a result of acetophenone coupling. 相似文献
97.
Summary In general, solid particles liquify when they are exposed to air laden with the vapor of a liquid in which they are soluble. There are exceptions, however, which may be explained by assuming the formation of a solvate.
On the occasion of the hundredth return ofFriedrich Emich's birthday.
The authors wish to express their appreciation to ProfessorO. F. Steinbach for his suggestions and advice. 相似文献
Zusammenfassung Feste Teilchen verflüssigen sich im allgemeinen, wenn sie Luft ausgesetzt sind, die mit dem Dampf einer Flüssigkeit geladen ist, in der sie löslich sind. Es wurden aber Ausnahmen gefunden, die möglicherweise durch die Bildung von Solvaten erklärt werden können.
Résumé Généralement, les particules solides se liquéfient si elles sont exposées à l'air chargé de la vapeur d'un liquide dans lequel elles sont solubles. Il existe cependant des exceptions que l'on peut expliquer en supposant la formation de solvates.
On the occasion of the hundredth return ofFriedrich Emich's birthday.
The authors wish to express their appreciation to ProfessorO. F. Steinbach for his suggestions and advice. 相似文献
98.
In contrast to lower phosphorylation states (e.g. the tryptic monophosphopeptide FQpSEEQQQTEDELQDK from bovine beta-casein), the specific detection of multi-phosphorylated peptides (e.g. the tetraphosphopeptide RELEELNVPGEIVEpSLpSpSpSEESITR from tryptic digestion of bovine beta-casein) has often been problematic for liquid chromatographic mass spectrometric (LC/MS) analysis owing to their high affinity for adsorption to exposed surfaces. We observed an enhancement in the overall detection of phosphopeptides on addition of phosphoric acid (0.1-1.0%) to the sample solution; a 10-fold increase in sensitivity was determined for the detection of two tryptic phosphopeptides and also a significant improvement in the detection of the tetraphosphopeptide. Using capillary LC with ion trap tandem MS for detection and identification, the achievable detection limits were 50 fmol and 50 pmol for the monophosphopeptide and the tetraphosphopeptide, respectively. Phosphoric acid is believed to act as a blocking agent to available silanol groups on both the silica capillary surface and the C(18)-bonded stationary phase silica surface. 相似文献
99.
Sportsman JR Daijo J Gaudet EA 《Combinatorial chemistry & high throughput screening》2003,6(3):195-200
Fluorescence polarization (FP) has become widely employed for high throughput screening used in pharmaceutical drug discovery. Assays of important signal transduction targets are now adapted to FP. In this review we examine assays for cyclic adenosine monophosphate, phosphodiesterases, and protein kinases and phosphatases using FP competitive immunoassays and a direct enzymatic method called IMAP. 相似文献
100.