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961.
Ryoichi Kishi Hideyuki Kihara Toshiaki Miura Hisao Ichijo 《Radiation Physics and Chemistry》2005,72(6):679-685
We prepared thermoresponsive and microporous polymer hydrogels by γ-ray irradiation of aqueous solutions poly(vinyl methyl ether) (PVME) at different heating rates. Under all temperature programs, opaque and heterogeneous PVME gels formed, which swelled at temperatures below the lower critical solution temperature and shrank at temperatures above it. All of the samples contained porous and phase-separated structures. The shape and size of the gel pores varied depending on the temperature programs. Gels having a sponge-like continuous porous structure formed only when the radiation-induced crosslinking was carried out at an optimum heating rate, which we found to be 0.11–0.13°C min−1. For temperature changes between 10°C and 40°C, gels with this structure showed rapid volume transitions on a time scale of about a minute. 相似文献
962.
Miura K Wang D Matsumoto Y Fujisawa N Hosomi A 《The Journal of organic chemistry》2003,68(22):8730-8732
The Et3B-initiated reaction of gamma-unsubstituted propargyl alcohols with dibutylchlorostannane (Bu2SnClH) at low temperature gave (Z)-vinylstannanes with high regio- and stereoselectivity. The corresponding alkyl propargyl ethers also underwent regio- and stereoselective homolytic hydrostannylation with Bu2SnClH; however, the regioselectivity was not so high as that with the propargyl alcohols. 相似文献
963.
Nobuaki Miura Takeshi Noro Fukashi Sasaki You Osanai 《Theoretical chemistry accounts》1998,99(4):248-254
The electron affinities of the Sc and Ti atoms have been obtained by configuration interaction calculations. Energy convergence
with respect to the systematic expansion of both the one-electron basis set and the configuration space was investigated for
valence electrons, and the inclusion of correlation contributions from core electrons and relativistic effects gave the electron
affinities of 0.181 eV and 0.163 eV for Sc and Ti, respectively. These are in excellent agreement with the observed values
of 0.189 ± 0.020 eV and 0.080 eV. The same approach was applied for the first excited states and positive ions of both atoms.
Excellent agreement with the experimental results was also obtained for these states.
Received: 16 February 1998 / Accepted: 2 April 1998 / Published online: 23 June 1998 相似文献
964.
Heterogeneous hydrogels were prepared by -ray irradiation of aqueous solutions of N-isopropylacrylamide (NIPAAm) and acrylic acid (AAc) having various compositions above the lower critical solution temperature. The structures of the poly(N-isopropylacrylamide) (PNIPAAm) gel and poly(NIPAAm-co-AAc) gels in both their highly hydrated and their natural states were observed by environmental scanning electron microscopy. The heterogeneous structures of the homopolymer gel and the copolymer gels whose AAc contents were between 10–50% consisted of interconnected microspheres. In the copolymer gel with a high AAc content, the structure became a largely interconnected one which lacked micro-droplets. The hydrophobic interaction caused by hydrogen bonding between the unionized carboxylic acid groups of AAc and the amide groups of NIPAAm, the rates of polymerization, and the aggregation rates play important roles in the formation of interconnected microsphere gel structures. 相似文献
965.
The first synthesis of allenylselenonium salts and their reactivities are described. The corresponding allenyl methyl selenides were alkylated with methyl trifluoromethanesulfonate to afford the desired compounds. Their reactions with active methylene carbanions produced furan, dihydrofuran or methylene cyclopropane derivatives via the Michael addition of nucleophiles to the selenonium salts. 相似文献
966.
The solid ion-pair material produced from the reaction between benzyldimethyltetradecylammonium chloride (BDTA) and sodium perchlorate on naphthalene provides the basis for a simple, rapid and selective technique for pre-concentrating iron from up to 500 ml of aqueous solution. Iron reacts with disodium 1-nitroso-2-naphthol-3,6-disulphonate (Nitroso-R salt) to form a water-soluble coloured chelate anion. The iron chelate anion forms a water-insoluble, stable iron-Nitroso-R-BDTA complex on naphthalene packed in a column. Trace amounts of iron are quantitatively retained on naphthalene in the pH range 3.5-7.5 and at a flow-rate of 1-2 ml min-1. The solid mass is dissolved out from the column with 5 ml of N,N-dimethylformamide and iron is determined by means of an atomic absorption spectrometer at 248 nm. The calibration graph is linear for concentrations of iron over the range of 0.5-20 micrograms in 5 ml of final solution. The standard deviation and relative standard deviation were calculated. The detection limit of the method was 0.0196 micrograms ml-1 of iron. The sensitivity for 1% absorption was 0.072 microgram ml-1 (0.165 microgram ml-1 by direct atomic absorption spectrometry of aqueous solution). The proposed method was applied to the determination of iron in standard alloys and biological samples. 相似文献
967.
A Hiraoka S Koike S Sakaguchi Y Masuda F Terai I Miura T Kawasaki H Kawai M Sakakibara 《Chemical & pharmaceutical bulletin》1989,37(10):2744-2746
Four (in total) compounds with inhibitory effects on the activity of bovine serum monoamine oxidase were isolated from the methanol-water extracts of Rhei Rhizoma (Daiou) and Sennae Folium (Senna), and identified as sennosides A, B, E and F. Among them, sennosides A and B were obtained from both Rhei Rhizoma and Sennae Folium, while sennosides E and F were detected only in the former. The 50% inhibitory concentrations of the four sennosides were 17, 9, 24 and 13 microM, respectively, and the type of inhibition by seenosides A and B with respect to allylamine as the substrate was non-competitive. 相似文献
968.
Development of radioimmunoassay of intact laminin and its clinical evaluation as a tumor marker. 总被引:2,自引:0,他引:2
The concentration of laminin including laminin variants in serum samples was measured by a double-antibody radioimmunoassay using intact laminin. The mean level in 92 normal subjects (47 men and 45 women) was defined as 1 unit (U)/ml, and the cut-off value (2 S.D. above the mean) was 1.37 U/ml. Mean laminin level in 391 patients with various malignancies was 1.50 +/- 0.86 U/ml. Laminin levels were elevated in various cancer patients, and in 45.0% (176/391) the values exceeded the cut-off level; in patients with cancer of the stomach or pancreas, positivity rate exceeded 60%. Mean laminin concentration for 130 pregnant women (2.06 +/- 0.65 U/ml) was also significantly higher than that of normal controls, but concentrations for patients with various benign diseases were within a low range (0.55 +/- 0.29-1.10 +/- 0.29 U/ml). In the stomach or pancreas cancer patients, a positive correlation between laminin level and tumor progression or course of the disease was observed. These findings indicate that serum laminin level is potentially useful in the diagnosis and monitoring of certain cancers. 相似文献
969.
Indole-1(and 3)-N,N-dimethylthiocarboxamide, 3-(1-pyrrolidinothiocarbonyl)indole and -1-methylindole (HL) react with hexachlorotetrakis(tri-n-butylphosphine)dirhodium(III) to give cyclorhodated complexes, [Rh(L)Cl2(PBu3)2] with L acting as a C—S chelate ligand (PBu3 = tri-n-butylphosphine) and indole-2-N,N-dimethylthiocarboxamide forms [Rh(L)Cl2(PBu3)2] with L acting as an N—S chelate. 1-Methylindole-2-N,N-dimethylthiocarboxamide and 2-(1-pyrrolidinothiocarbonyl)-1-methylindole did, however, not react under similar conditions. The complexes were characterized by spectroscopic methods and the structures of the four complexes with HL = indole-1- and 3-N,N-dimethylthiocarboxamide, and 3-(1-pyrrolidinothiocarbonyl)indole and -1-methyl-indole were confirmed by X-ray analysis. The octahedral complex [Rh(L)Cl2(PBu3)2] had trans-(PBu3)2 and cis-(Cl)2 arrangements and L was coordinated through the S and indole ring C2 atoms to form a five-membered chelate ring. The unreactivity of 1-methylindole-2-N,N-dimethylthiocarboxamide and 2-(1-pyrrolidino)thiocarbonyl-1-methyl-indole may be due to steric hindrance caused by the additional 1-methyl substituent. 相似文献
970.
Determination of sulfur oxyanions by ion chromatography on a silica ODS column with tetrapropylammonium salt as an ion-pairing reagent 总被引:1,自引:0,他引:1
The difficulty in using conventional ion chromatography for the determination of sulfate, thiosulfate, dithionate and polythionates (tri-, tetra-, penta- and hexathionate) in their mixtures, comes mainly from very late elutions of polythionates due to their strong retentions onto a separating column. Rapid and sensitive determination of these sulfur oxyanions has been achieved by ion-pair chromatography using a silica octadecylsilane (ODS) column with mobile phases of 10% or 20% (v/v) acetonitrile in water (pH, 5.0) containing 0.2 mM phthalate and 7 mM tetrapropylammonium salt (TPAOH). The sulfur species separated on the column were monitored with a conductivity detector after passing through a micro membrane suppressor in the H+ form. When an acetonitrile-water (10:90, v/v) mobile phase (pH, 5.0) of 0.2 mM phthalate and 7 mM TPAOH was used at a flow-rate of 0.8 ml min−1, sulfate, thiosulfate, dithionate and trithionate were eluted at short retention times of 9.1, 9.7, 11.4 and 15.8 min, respectively; however, the higher polythionates required more than 30 min to elute. When the concentration of acetonitrile in the mobile phase was raised to 20% (v/v), all polythionates of tri- to hexathionate were completely separated from their mixtures within 21 min; in this instance, both sulfate and thiosulfate failed to be resolved due to their close retention times. Good recoveries were obtained for these sulfur oxyanions when added to various hot-spring water samples. 相似文献