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21.
Changes in the mass spectra with inlet temperature were used in this work to demonstrate the dependence of keto-enol tautomerism of acetylacetone, 3-methyl acetylacetone and 3-allyl acetylacetone on temperature. The largest dependence of temperature were shown by the ion [M ? 42]+. arising from a McLafferty type rearrangement and by the ion [M ? Me]+ resulting from simple α-cleavage. The ion [M ? 42]+. peak increases with the temperature of the inlet system while the ion [M ? Me]+ peak decreases. By assuming that the ion [M ? 42]+. represents the keto form and that the ion [M ? Me]+ represents the cis-enol form (stabilized by the hydrogen bond) one sees that the direction of the intensity variation of these peaks with temperature is in accord with the expected change of keto-enol tautomerism with temperature. A quantitative correlation on the basis of the above assumptions is also approached. Recording of the mass spectra of these three β-diketones at different energies of the incident electrons enables us to estimate whether or not the particular ions present in the mass spectra result from energetically favourable processes. The variation of the intensities of the peaks with the temperature of the inlet at different electron energies is also discussed. 相似文献
22.
23.
Michael P. Hartshorn Richard G. Jensen A. Grant Waller Graeme J. Wright 《Tetrahedron letters》1987,28(52):6701-6704
Reaction of the 15N-4-nitrodienone (1) with excess nitrogen dioxide in benzene for 16 h gives the 4,5,6-trinitro ketone (2), labelled (15NO2) at C6 but not at C4, and recovered 4-nitrodienone (1) in which extensive loss of 15NO2 has occurred. The mechanistic implications of these and related results are discussed. 相似文献
24.
Li W Nelson DP Jensen MS Hoerrner RS Javadi GJ Cai D Larsen RD 《Organic letters》2003,5(25):4835-4837
Imidazo[1,2-a]pyrimidine can be arylated at the 3-position with aryl bromides in the presence of base and a catalytic amount of palladium. This provides an efficient one-step synthesis of 3-arylimidazo[1,2-a]pyrimidines from the unsubstituted heterocycle. [reaction: see text] 相似文献
25.
A kinetic method for the simultaneous determination of magnesium and calcium ions in solution is described. The method is based on the dissociation reactions of cryptand (2.2.2) complexes; a stopped-flow injection technique is used with spectrophotometric monitoring of the phthalein complexone complexes of the released metal ions. Analyses were done at a rate of 80 h?1, with injected sample volumes of 80 μl. A microcomputer system for data acquisition and control of the system is described. 相似文献
26.
For identification of cysteine residues on microsequence analysis it is crucial to derivatize the sulfhydryl groups. This reaction requires a desalting step which often represents a major obstacle, especially if the sample consists of limited amounts of a hydrophobic membrane protein. An alkylation procedure is described, allowing efficient derivatization (greater than 90%) of cysteines and cystines even in low microgram quantities, as revealed by test analyses with lysozyme and a hydrophobic membrane protein. The modified protein is recovered in high yields in a form suitable for both microsequence analysis and amino acid analysis. The method involves electrophoretic desalting by miniaturized Tricine-sodium dodecyl sulfate-polyacrylamide gel electrophoresis and in situ alkylation after electro-transfer onto polyvinylidene difluoride membranes. Precautions against NH2-terminal blocking during sample preparations are provided. The general applicability of the method is illustrated by the structural characterization of the low abundance membrane receptor for human urokinase plasminogen activator. 相似文献
27.
Klapars A Waldman JH Campos KR Jensen MS McLaughlin M Chung JY Cvetovich RJ Chen CY 《The Journal of organic chemistry》2005,70(24):10186-10189
[reaction: see text] A mild and transition-metal-free method for the alpha-arylation of aliphatic nitriles with activated heteroaryl halides was developed using NaHMDS or KHMDS as base at ambient temperature. The key to the success of this method is generation of the nitrile anion in the presence of the heteroaryl halide. The method is applicable to both primary and secondary carbonitriles and a wide range of heteroaryl halides. Selective monoarylation was observed with primary carbonitriles. The operational simplicity and the mild reaction conditions add to the value of this method as a practical alternative to the preparation of alpha-heteroaryl carbonitriles. 相似文献
28.
To better understand the process of multistage carcinogenesis in Schwann cells, we have attempted to isolate novel candidate genes involved in neoplastic progression of mouse malignant Schwannoma cells. The semi-differentiated Schwannoma cell line 56-24 and the less differentiated Schwannoma cell line 64-39 were established from peripheral nerve sheath tumors arising in transgenic mice of the MBP/SV40 large T strain Tg29. By using the chemical cross-linking subtraction technique, we have cloned a novel murine cDNA that detects pronounced expression in 56-24 cells but not in 64-39 cells. The longest open reading frame of the cDNA predicts a peptide showing 95% amino acid sequence homology to the recorded sequence of the human immunophilin homolog huFKBPr38, one of a family of proteins that are thought to interface with a wide range of intracellular signal transduction systems. The predicted open reading frame of the corresponding gene, named muFKBP38, encodes a 38 kDa protein that harbors an FK-binding protein (FKBP) domain that is 36% identical to that of muFKBP52, a three-unit tetratricopeptide repeat and a consensus leucine-zipper repeat. Although muFKBP38 mRNA was detected in both neurons and glial cells, pronounced expression of the immunophilin homolog appeared in various classes of neurons associated with the hippocampal formation, as shown by in situ hybridization analysis of adult mouse brains. Taken together, these data indicate that muFKBP38 is (i) a novel potential marker for semi-differentiated Schwannomas, (ii) may form homomultimers and/or interact with other proteins, and (iii) may have a role in neurons associated with memory function. 相似文献
29.
Belofsky GN Anguera M Jensen PR Fenical W Köck M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(8):1355-1360
Three new oxepin-containing natural products (1-3) and two new fumiquinazoline metabolites (4-5) have been isolated from organic extracts of the culture broth and mycelia of an Acremonium sp., a fungus obtained from the surface of the Caribbean tunicate Ecteinascidia turbinata. The structures of the five compounds were determined through extensive analysis of 1D- and 2D-NMR data, and mass spectrometry. Compound 1 exhibited good anti-inflammatory activity in a topical RTX-induced mouse ear edema assay. Compounds 4 and 5 exhibited weak antifungal activity toward Candida albicans in a broth microdilution assay. 相似文献
30.
K M Jensen 《Journal of chromatography. A》1975,111(2):389-396
A gas chromatographic method with electron capture detection has been developed for the analysis of nitrazepam in serum. N-Desmethyldiazepam is used as internal standard. Nitrazepam isolated from serum is converted by acid hydrolysis into 2-amino 5 nitrobenzophenone, which is chromatographed. Metabolites of nitrazepam (7-amino and 7-acetamido compounds) are not included in the determination. Recovery experiments showed that the method is quantitative. The limit of detection is 5 ng/ml of nitrazepam in serum. The method has been used for measuring serum concentrations of nitrazepam in bioavailability studies on subjects given a single dose of nitrazepam tablets. 相似文献