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991.
Tsunoyama H Ohshimo K Misaizu F Ohno K 《Journal of the American Chemical Society》2001,123(4):683-690
Stabilities and intracluster reactions have been investigated by photoionization mass spectrometry for clusters composed of an alkali metal atom (M; Na and K) and acrylic ester molecules, CH(2)=CHCO(2)R, such as methyl acrylate (MA; R = CH(3)) and ethyl acrylate (EA; R = C(2)H(5)). The following two features are commonly observed in the photoionization mass spectra of M(CH(2)=CHCO(2)R)(n): (1) The ion with n = 3 is clearly observed as a magic number. (2) Fragmented cluster ions with the loss of ROH, [M(CH(2)=CHCO(2)R)(n) - ROH] are detected only for n = 3. These features are both explained by an intracluster oligomerization reaction initiated by electron transfer from the metal atoms. The magic number trimer is concluded to have the stable structure of cyclohexane derivatives as a result of oligomerization. The fragmentation reaction is explained by Dieckmann cyclization after anionic oligomerization to produce another isomer of the trimer. The intracluster electron transfer is also supported by theoretical calculation for Na(MA) based on density functional theory. 相似文献
992.
N Ohno T Miura K Saito M Nishijima T Miyazaki T Yadomae 《Chemical & pharmaceutical bulletin》1992,40(8):2215-2218
Physicochemical properties and antitumor activities of a fungal (1----3)-beta-D-glucan, OL-2, isolated from Leiwan (Omphalia lapidescens) were examined. OL-2 showed sharp signals on carbon-13 nuclear magnetic resonance spectrum in dimethylsulfoxide-d6 as a solvent, and these signals were significantly reduced by the addition of distilled water to the concentration of 20%. This phenomenon is consistent with the general property of the gel forming (1----3)-beta-D-glucan. Binding of OL-2 to Congo red induced a significant change of lambda max to a longer wavelength, and the concentration to induce gel to sol transition was about 0.7 N; in contrast, the concentration was about 0.2 N in the cases of SPG and curdlan. These observations suggested that the gel structure would be significantly stabilized in the case of OL-2. OL-2 showed no or low antitumor activity against the solid form of Sarcoma 180 by intraperitoneal and intralesional administrations; however, it was effective on the ascites form of Sarcoma 180. Of interest, OL-2 also showed significant antitumor activity against the ascites form of MH-134 when administered with 5-fluorouracil. These results indicated that OL-2 showed characteristic features regarding its physicochemical properties and antitumor activity. 相似文献
993.
Change of biological activities of (1----3)-beta-D-glucan from Grifola frondosa upon molecular weight reduction by heat treatment 总被引:2,自引:0,他引:2
Changes of biological activities manifested by (1----6)-branched (1----3)-beta-D-glucans of various molecular weights obtained by heat treatment of the corresponding intact beta-glucan at 150 degrees C (HD-LE) were examined. The activities assessed in this study were as follows: an antitumor activity, activation of alternative complement pathway, glucose consumption by macrophages, macrophage-mediated lysosomal enzyme activity in culture supernatant and cell lysate, interleukin-1 (IL-1) activity, and adjuvant activity. HD-LE could be classified into three groups: 1) HD-LE 0 h (MW 800000) which activated all of the biological activities tested, 2) HD-LE 0.5 and 3 h (MW 250000 and 21000) which lacked or exhibited low levels of activities such as activation of alternative complement pathway and lysosomal enzyme secretion, 3) HD-LE 6 h (MW 6400) which only activated glucose consumption and synthesis of lysosomal enzyme. These results suggest that an antitumor glucan is not always a multiple enhancer of host defense mechanisms and that a large molecular weight is required to augment multiple immunological activities. 相似文献
994.
Otani Y Nagae O Naruse Y Inagaki S Ohno M Yamaguchi K Yamamoto G Uchiyama M Ohwada T 《Journal of the American Chemical Society》2003,125(49):15191-15199
Here we show that amides of bicyclic 7-azabicyclo[2.2.1]heptane are intrinsically nitrogen-pyramidal. Single-crystal X-ray diffraction structures of some relevant bicyclic amides, including the prototype N-benzoyl-7-azabicyclo[2.2.1]heptane, exhibited nitrogen-pyramidalization in the solid state. We evaluated the rotational barriers about the amide bonds of various N-benzoyl-7-azabicyclo[2.2.1]heptanes in solution. The observed reduction of the rotational barriers of the bicyclic amides, as compared with those of the monocyclic pyrrolidine amides, is consistent with a nitrogen-pyramidal structure of 7-azabicyclo[2.2.1]heptane amides in solution. A good correlation was found between the magnitudes of the rotational barrier of N-benzoyl-7-azabicyclo[2.2.1]heptanes bearing para-substituents on the benzoyl group and the Hammett's sigma(p)(+) constants, and this is consistent with the similarity of the solution structures. Calculations with the density functional theory reproduced the nitrogen-pyramidal structures of these bicyclic amides as energy minima. The calculated magnitudes of electron delocalization from the nitrogen nonbonding n(N) orbital to the carbonyl pi orbital of the amide group evaluated by application of the bond model theory correlated well with the rotational barriers of a variety of amides, including amides of 7-azabicyclo[2.2.1]heptane. The nonplanarity of the amide nitrogen of 7-azabicyclo[2.2.1]heptanes would be derived from nitrogen-pyramidalization due to the CNC angle strain and twisting of the amide bond due to the allylic strain. 相似文献
995.
Aromatic isothiosemicarbazones 1–4 underwent disproportionation at elevated temperature in the presence of a thiol or a thiol-releasing substance to give 1-arylmethylene-3-alkylthio-5-aryl-1H-1,2,4-triazole derivatives 6–9 in moderate yields. An isothiosemicarbazone of aliphatic aldehyde with no α-hydrogen did not give rise to the corresponding disproportionation under the similar conditions. Cross reaction occurred between two different isothiosemicarbazones but the cross compound could be isolated only in a poor yield. Any inert solvent markedly inhibited the disproportionation reaction even only with a slight dilution. A tentative reaction mechanism, in which it might involve a potential nitrene-sulfonium ion pair as a key step, is presented. 相似文献
996.
The properties of quaternary ammonium salt-type cationic trimeric surfactants (m-2-m-2-m, m represents the carbon atom number in alkyl chain lengths of 8, 10, and 12) and oppositely charged anionic monomeric surfactant, sodium n-octyl sulfate (SOS), were characterized by employing several techniques such as static surface tension, fluorescence spectroscopy, and dynamic light-scattering measurements. The critical micelle concentrations (cmc) of m-2-m-2-m were much lower than those of the corresponding dimeric and monomeric surfactants, and decreased with increasing chain length. The addition of SOS to m-2-m-2-m solutions resulted in a further decrease of the cmc. The mixed surfactants showed higher efficiencies in lowering the surface tension than the individual surfactants. The fluorescence measurements suggested the formation of mixed micelles with a hydrophobic environment in the solutions even at lower concentrations. The dynamic light-scattering study indicated the presence of two different kinds of aggregates with different hydrodynamic diameters. The larger one was attributed to the mixed micelle of m-2-m-2-m and SOS. These results indicated a decline of the electrostatic repulsion between cationic head groups through the incorporation of anionic surfactant into the mixed surfactants. 相似文献
997.
A versatile chiral synthon, (1R,6S)-6-methoxycarbonyl-3-cyclohexene-1-carboxylic acid, was obtained by an enantioselective hydrolysis of the corresponding meso diester with pig liver esterase. This enzymatic hydrolysis can easily be carried out on a multi-hundred gram scale. The chiral monoester thus obtained can be further converted into all stereoisomers of 1-amino-2-alkoxycarbonyl-4-cyclohexene derivatives in an enantio- and stereocontrolled manner. These derivatives are considered as potential key intermediates for synthesizing a variety of biologically interesting compounds such as aminocyclitol and carbapenem antibiotics. 相似文献
998.
The cofactor requirement of purified 20 beta-hydroxysteroid dehydrogenase from cytosol fraction of neonatal pig testis, in the reduction of 17 alpha-hydroxyprogesterone was investigated. The enzyme required beta-nicotinamide adenine dinucleotide phosphate, reduced form (beta-NADPH) as the preferred cofactor, with an apparent Km value of 17 microM. Furthermore, alpha-nicotinamide adenine dinucleotide phosphate, reduced form (alpha-NADPH), beta-3'-NADPH and beta-nicotinamide adenine dinucleotide (beta-NADH) were also utilized as hydrogen donors in the reduction at relatively high concentration with apparent Km values of 85.2 microM, 179.2 microM and 1.00 mM, respectively. The optimum pH was 5.5 when beta-NADPH was used as the cofactor, while it was 6.0 when beta-NADH was used. The hydrogen transfer from the beta-NADPH to the product, 17 alpha,20 beta-dihydroxypregn-4-en-3-one catalyzed by 20 beta-hydroxysteroid dehydrogenase was stereospecific, and the 4-pro-S-hydrogen of the nicotinamide moiety was transferred to the product. 相似文献
999.
Chemo- and stereoselectivity in the ring-opening reaction of epoxides with a reagent prepared from allylmagnesium halide and chlorotitanium triphenoxide is described. It has been proven that the allylating reagent can also be used for the reaction of epoxides bearing a tert-butyl ester, amide, or acetal moiety, and that the epoxide cleavage regioselectively takes place at the more substituted carbon in all cases. Interestingly, while the reaction of acyclic 2,2,3-trialkyl epoxides or 3,3-disubstituted 2,3-epoxy alcohol derivatives with the allyltitanium reagent yielded the allylated products as an almost 1:1 diastereomixture, the ring-opening reaction of 2-substituted 2,3-epoxy alcohol derivatives stereospecifically proceeded through the anti pathway. The latter reaction is extremely useful for asymmetric construction of quaternary carbon centers. 相似文献
1000.
Mami Ohno Toshikazu Takata Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》1995,33(15):2647-2655
Synthesis of 1,5-bis(4-fluorobenzoyl)-2,6-dimethylnaphthalene ( 1 ), polycondensation of 1 with Bisphenol A, and properties of the obtained polymer were studied. Friedel–Crafts acylation of 2,6-dimethylnaphthalene with 4-fluorobenzoyl chloride in nitrobenzene selectivity afforded 1 in 82% yield. X-ray single crystal structural analysis of 1 confirmed that the dibenzoylation proceeded regioselectively and two methyl groups sterically inhibited the coplanarity of the two aromatic planes. The polycondensation of 1 with Bisphenol A in toluene/N-methyl-2-pyrrolidone (NMP) mixed solvent in the presence of excess potassium carbonate as a condensation reagent was carried out at 180°C for 4 h to quantitatively afford the corresponding poly(arylene ether-ketone) (PEK) 3 with high molecular weight (M?n~30,000) as a slightly yellow powder. As the reaction time was prolonged, both M?n and MWD of 3 increased and the solubility of 3 in chloroform clearly decreased. By GPC-LALLS, M?n of 3 obtained by the polycondensation for 16 h, was 85,000. The PEK 3 with high molecular weight was produced in a quantitative yield in a variety of solvents such as sulfolane. Water formed during the polycondensation hardly affected the yield and molecular weight of 3 , although a small molecular weight decrease took place. To evaluate the special effect of the methyl groups of 3 , polycondensation of 2,6-bis(4-fluorobenzoyl)naphthalene 2 with bisphenol A was carried out for comparison and the corresponding PEK 4 was quantitatively obtained. Whereas 3 was soluble in ordinary organic solvents such as tet-rahydrofuran (THF), chloroform, and NMP at room temperature, 4 was insoluble in most solvents except for strong acids such as conc. sulfonic acid. The polymer 3 showed high glass transition temperature (238°C) and 5% weight loss temperature (457°C). Casting of the polymer from THF solution gave a transparent, tough, flexible, and amorphous film. © 1995 John Wiley & Sons, Inc. 相似文献