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61.
Thermal nitrogen extrusion of 2-methylene-6,7-diazabicyclo[3.2.2]non-6-enes and 6,7- diazabicyclo[3.2.2]nona-2,6-diene,6 proceeded easily to give closure and cleavage products the corresponding 5-methylene-1,4-cycloheptylenes and 4-cyclohepten-1,3-ylenes, respectively. 相似文献
62.
Takako Takahashi 《Journal of polymer science. Part A, Polymer chemistry》1970,8(3):739-749
A peculiar copolymer composition equation applicable to the radical copolymerization of 1,1-dichloro-2-vinylcyclopropane with monosubstituted ethylenes was developed. The theory was applied to such ethylenes as methyl acrylate, methyl methacrylate, and styrene. The reactivity ratio parameters which give the best fit to the experimental data were determined. 相似文献
63.
Matsumori N Yamaji N Matsuoka S Oishi T Murata M 《Journal of the American Chemical Society》2002,124(16):4180-4181
Polyenemacrolides such as amphotericin B (AmB) were thought to assemble together and form an ion channel across plasma membranes. Their antimicrobial activity has been accounted for by this assemblage, whose stability and activity are dependent on sterol constituents of lipid bilayer membranes. The structure of this channel-like assemblage formed in biomembranes has been a target of extensive investigations for a long time. For the first step to this goal, we prepared several AmB dimers with various linkers and tested for their channel-forming activity. Among these, AmB dimers that bore an aminoalkyl-dicarboxylate tether covalently linked between amino groups of AmB showed potent hemolytic activity. Furthermore, K+ influx actions monitored by measuring the pH of the liposome lumen by 31P NMR revealed that the dimers formed the molecular assemblage similar to that of AmB in phospholipid membrane. Judging from changes in 31P NMR spectra, the dimers appeared to induce "all-or-none"-type ion flux across the liposome membrane in the presence of ergosterol, which suggested that the ion channel formed by ergosterol/dimer is similar to that of AmB. With these data in hand, we are now trying to elucidate the structure of the ion-channel complex by making the labeled conjugates of AmB for NMR measurements. 相似文献
64.
Yoh Kodera Ayako Ajima Katsunobu Takahashi Ayako Matsushima Yuji Saito Yuji Inada 《Photochemistry and photobiology》1988,47(2):221-223
Abstract— Hematoporphyrin, having two carboxylic groups, was coupled with α-(3-aminopropyl)-ω-methoxypoly(oxyethylene), PEG-NH2 , through acid-amide bond formed with carbodtimide. PEG-modified hematoporphyrin was readily soluble not only in neutral aqueous solution but also in organic solvents. Its absorption spectrum showed a sharp band at 376 nm in neutral aqueous solution and at 403 nm in benzene. Modified hematoporphyrin acted as a photosensitizer; imidazole and indole were photooxidized in organic solvents such as benzene or chloroform, and uric acid was also photooxidized in neutral aqueous solution. 相似文献
65.
Shuntaro Mataka Akira Hosoki Kazufumi Takahashi Masashi Tashiro 《Journal of heterocyclic chemistry》1980,17(8):1681-1685
The reaction of tetrasulfur tetranitride ( 1 ) with various aryl and alkyl benzyl ketones ( 2a-o ), oxindole ( 11 ), benzyl α-pyridyl ketone ( 12 ) and α-phenacylpyridine ( 13 ) afforded the corresponding 1,2,5-thiadiazoles ( 3a-n, 11 and 14 ). The scope and limitations of the above reaction were investigated and the evidences suggesting the radical anion mechanism are presented. 相似文献
66.
R. Minayoshi T. Ohyama N. Kinugawa J. Kamishima T. Ogi K. Ishikawa M. Noguchi H. Suganuma K. Takahashi S. Enomoto M. Yanaga 《Journal of Radioanalytical and Nuclear Chemistry》2007,272(2):429-431
The concentrations of essential trace elements and proteins in cytosolic fraction of hepatic cells of mice fed with Zn-deficient
diet (Zn-def, mice) and control were determined by ICP-MS and BCA protein assay method, respectively, after division into
forty fractions by gel filtration chromatography. The concentrations of zinc and proteins decreased in the 14–17th fractions
of Zn-def, mice, whereas cobalt concentrations increased in the 14, 17, and 18th fractions. However, no significant differences
were found on the gel after SDS-PAGE for the 12–21st fractions, although the BCA protein assay date showed the decrease of
protein amounts in 13–15th fractions of Zn-def. mice. 相似文献
67.
Tanaka K Ding MY Helaleh MI Taoda H Takahashi H Hu W Hasebe K Haddad PR Fritz JS Sarzanini C 《Journal of chromatography. A》2002,956(1-2):209-214
In this preliminary study, a new approach to ion-exclusion chromatography is proposed to overcome the relatively poor conductivity detection response which occurs in ion-exclusion chromatography when acids are added to the eluent in order to improve peak shape. This approach, termed vacancy ion-exclusion chromatography, requires the sample to be used as eluent and a sample of water to be injected onto a weakly acidic cation-exchange column (TSKgel OApak-A). Vacancy peaks for each of the analytes appear at the retention times of these analytes. Highly sensitive conductivity detection is possible and sharp, well-shaped peaks are produced, leading to efficient separations. Retention times were found to be affected by the concentration of the analytes in the eluent, and also by the presence of an organic modifier such as methanol in the eluent. Detection limits for oxalic, formic, acetic, propionic, butyric and valeric acids were 0.1, 0.2, 0.3, 0.3, 0.4 and 0.5 microM, respectively, and linear ranges for some acids extended over two orders of magnitude. Precision values for retention times were 0.21% and for peak areas were <1.90%. The vacancy ion-exclusion chromatography method was found to give detection responses four to 10 times higher than conventional ion-exclusion chromatography using sulfuric acid eluent and two to five times higher than conventional ion-exclusion chromatography using benzoic acid eluent. 相似文献
68.
Amphotericin B (AmB 1) is known to assemble together and form an ion channel across biomembranes. The antibiotic consists of mycosamine and macrolactone moieties, whose relative geometry is speculated to be determinant for the drug's channel activity and sterol selectivity. To better understand the relationship between the amino-sugar orientation and drug's activity, we prepared conformation-restricted derivatives 2-4, in which the amino and carboxyl groups were bridged together with various lengths of alkyl chains. K+ influx assays across the lipid-bilayer membrane revealed that ergosterol selectivity was markedly different among derivatives; short-bridged derivative 2 almost lost the selectivity, while 3 showed higher ergosterol preference than AmB itself. Monte Carlo conformational analysis of 2-4 based on NOE-derived distances indicated that the amino-sugar moiety of 2 comes close to C41 because of the short bridge, whereas those of 3 and 4 are pointing outward. The mutual orientation of the amino-sugar moiety and macrolide ring is so rigid in derivatives 2 and 3 that these conformations should be unchanged upon complex formation in lipid membranes. These results strongly suggest that the large difference in sterol preference between derivatives 2 and 3 is ascribed to the different orientation of amino-sugar moieties. These findings allowed us to propose a simple model accounting for AmB-sterol interactions, in which hydrogen bonding between 2'-OH of AmB and 3beta-OH of ergosterol plays an important role. 相似文献
69.
Alkyl halides underwent unique cross-coupling reaction with vinylmagnesium chloride in the presence of Ni catalyst to give 2-alkyl-3-butenyl Grignard reagent (1) in high yields. This reaction proceeded efficiently at 25 degrees C in THF using primary and secondary alkyl fluorides. On the other hand, PhCH=CHMgBr gave double alkylative vinyl coupling product 4 in good yield as the sole coupling product. Alkyl fluorides react as the most suitable alkylating reagent in comparison to the corresponding chlorides, bromides, and iodides. 相似文献
70.
An automatic method for the determination of metabolites of Ropivacaine in urine was set up. It utilizes supported liquid membrane extraction for sample clean-up and enrichment, followed by ion-pair chromatography determination using UV detection. The extraction was very selective with no observed interfering compounds from the urine matrix, permitting simple isocratic chromatographic analysis. The detection limits for spiked urine samples were 2–18 nM for the different compounds. The repeatability was 1–3% (RSD) with an internal standard that was also extracted, and about twice without this standard. A throughput of 3.3 samples per hour was achieved and the liquid membrane was stable for more than a week. 相似文献