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Kinetics of chemiluminescence reactions of 2-methyl-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one (1c, Cypridina luciferin analogue) and substituent effects of the 6-aryl group of derivatives 1 strongly suggest that the rate-determining step is a single electron transfer from an anion derived from 1 to a triplet molecular oxygen (O2) in the oxygenation process. 相似文献
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Hepatoprotective and hepatotoxic actions of oleanolic acid-type triterpenoidal glucuronides on rat primary hepatocyte cultures 总被引:2,自引:0,他引:2
Kinjo J Okawa M Udayama M Sohno Y Hirakawa T Shii Y Nohara T 《Chemical & pharmaceutical bulletin》1999,47(2):290-292
The protective effects of oleanolic acid-type saponins and their derivatives on in vitro immunological liver injury of primary cultured rat hepatocytes were studied. A known antihepatotoxic saponin (chikusetsusaponin IVa, 1) showed hepatoprotective activity in this model. Although a rhamnosyl derivative (2) of 1 similarly showed hepatoprotective activity, its prosapogenin (5) did not show any hepatoprotective activity. On the contrary, 5 exhibited cytotoxicity toward liver cells. In the absence of antiserum, monodesmosyl saponins showed hepatotoxicity, while the bisdesmosyl saponins except for 1, did not show such hepatotoxicity. In order to clarify the effects of the sugar residues at C-3 and C-28 responsible for hepatoprotective and hepatotoxic actions, oleanolic acid 3-O-glucuronide (2a) and oleanolic acid 28-O-glucoside (2b) were prepared and tested. 2b showed neither hepatoprotective action nor hepatotoxicity. In contrast, 2a was effective at 90 microM on hepatoprotection, although it showed strong hepatotoxicity. Oleanolic acid (2c) itself showed both hepatoprotective action and weak hepatotoxicity. Therefore, the hepatoprotective activity of these types of saponins could represent a balance between hepatoprotective action and hepatotoxicity. 相似文献
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Eiichi Kobayashi Shojiro Kaita Sadahito Aoshima Junji Furukawa 《Journal of polymer science. Part A, Polymer chemistry》1995,33(13):2175-2182
Homo- and copolymerizations of butadiene (BD) and styrene (St) were carried out by gadolinium catalysts having various tricarboxylate ligands [Gd(OCOR)3: R = CH3, CH2Cl, CHCl2, CCl3, and CF3], to investigate the effects of ligands and discuss the cis polymerization mechanism. Polymerization of BD with Gd(OCOR)3—(i—Bu)3Al—Et2AlCl catalysts was carried out in hexane at 50°C. By each catalyst, poly(BD) having a high cis content (cis = 97–99%) in 22–85% yields for 2–24 h were obtained. The ligands with low pKa values increased the polymerization activity as follows: R of Gd(OCOR)3: CF3 > CCl3 > CHCl2 > CH2Cl ~ CH3. On the other hand, in the polymerization of St or copolymerization of BD and St under similar conditions, the highest activity was attained by a Gd(OCOCCI3)3- based catalyst. The difference in the optimum ligand among the homo- and copolymerization of BD and St was discussed on the basis of energy levels of the catalysts. In the copolymers of BD and St, the cis-1,4 content of the BD unit decreased with increasing St content. Furthermore, according to the diad analysis of copolymers (St content ~ 14.5 mol %) by 13C NMR spectroscopy, the low cis value of the BD unit was observed in the St-BD diad (cis/trans/vinyl = 24/53/23), while the high cis value of the BD unit remained in the BD-BD diad (cis/trans/vinyl = 89/10/1). These results suggest that the terminal BD unit is controlled by the cis configuration by the coordination between the penultimate cis vinylene unit and the gadolinium metal catalyst, whereas the presence of the penultimate St unit interferes with cis polymerization of the terminal BD unit. The difference in the coordination mechanism in the course of polymerization between rare earth metal and transition metal catalysts such as the Ni(acac)2 and Co(acac)3-based catalyst was also discussed. © 1995 John Wiley & Sons, Inc. 相似文献
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Okawa M 《Physical review letters》1985,54(10):963-965
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A porphyrin nanotube: size-selective inclusion of tetranuclear molybdenum-oxo clusters 总被引:2,自引:0,他引:2
Harada R Matsuda Y Okawa H Kojima T 《Angewandte Chemie (International ed. in English)》2004,43(14):1825-1828
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Eguchi S Suzuki T Okawa T Matsushita Y Yashima E Okamoto Y 《The Journal of organic chemistry》1996,61(21):7316-7319
Both optical isomers of a quinazoline alkaloid, vasicinone, were synthesized by two different methods. The first method used (3S)-3-hydroxy-gamma-lactam as a chiral synthon, which was, after O-TBDMS protection, o-azidobenzoylated followed by treatment with tri-n-butylphosphine to afford (S)-(-)-vasicinone via the tandem Staudinger/intramolecualr aza-Wittig reaction. The second method utilized asymmetric oxygenation of deoxyvasicinone with (1S)-(+)- or (1R)-(-)-(10-camphorsulfonyl)oxaziridine (the Davis reagent), respectively. The aza-enolate anion of deoxyvasicinone was treated with (S)-(+)-reagent to afford (R)-(+)-vasicinone in 71% ee, while the reaction with (R)-(-)-reagent gave (S)-(-)-vasicinone in 62% ee. The optical purity was analyzed by HPLC on specially modified cellulose as a stationary phase. These results provided a facile method to prepare both optical isomers of vasicinone and confirmed the recently reversed stereochemistry of natural (-)-vasicinone. 相似文献