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31.
K Ichimura H Yamanaka K Chiba T Shinozuka Y Shiki K Saito S Kusano S Ameniya K Oyama Y Nozaki 《Journal of chromatography. A》1986,374(1):5-16
Until now, there has been little work covering all of the main native adrenal-cortical steroids in blood. We therefore established a method for the simultaneous quantitative measurement of 14 native adrenal-cortical steroids, which involves capillary column gas chromatography-mass spectrometry (GC--MS). Serum steroids were purified from serum with the Extrelut mini-column and then converted into stable derivatives for GC-MS by a combination of boronic cyclization and trimethylsilyl and methyloxime derivatization. The sensitivities (with a signal-to-noise ratio greater than or equal to 7) of our GC-MS method ranged from 0.1 to 1.0 ng/ml of serum, and the coefficients of variation of intra- and inter-assays were less than 19% for each steroid. Our newly devised method involving a capillary column GC-MS system has been proven to be a simple and suitable method for a diagnosis requiring simultaneous detection of many native adrenal steroids in clinical practice. The analysis time is only 4 h. 相似文献
32.
We implemented ab initio self‐consistent field (SCF) fractional occupation numbers (FON) calculation with Dunlap's interpolation scheme for the twisted ethylene, which is a prototype molecule of a σ–π biradical system. The calculational results are compared with those of complete‐active‐space (CAS) SCF and spin‐unrestricted Kohn–Sham (UKS) calculations on potential surfaces, occupation numbers of natural orbitals, and correlation entropies. It was found that the UKS methods gave similar results to CASSCF, while the FON solutions appeared in only the nearly complete degenerate region. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 93: 317–323, 2003 相似文献
33.
The Pt-Ir microelectrode modified through one step electropolymerization is proposed for the isocitrate amperometric biosensor construction. The enzyme (isocitrate dehydrogenase-ICDH), coenzyme (NADP(+)) and mediator (Meldola's Blue) were immobilized onto the microelectrode surface in one step from a PIPES buffer solution containing pyrrole. The optimized experimental conditions were 25 cycles of cyclic voltammetric in a solution containing 3.58 10(-5) mol l(-1) of mediator, 3.51 10(-4) mol l(-1) of coenzyme and 2.68 U ml(-1) of enzyme. In contrast to the biosensor for isocitrate reported in literature, just one enzyme was immobilized and no coenzyme addition in the solution of analysis was necessary. Catalytic currents were proportional to the isocitrate concentration between 7.7 10(-6) and 1.04 10(-4) mol l(-1), showing good repeatability. The detection limit of the proposed biosensor was 3.50 10(-6) mol l(-1), the response time was lower than 20 s, the lifetime was about 30 determinations and no significant interference of sugars and citric acid was verified. Orange juice samples were analysed by both methodology biosensor and spectrophotometric commercial kit, and the obtained results presented a good correlation. The data demonstrated that the developed biosensor is suitable for isocitrate determination in orange juice without matrix interferences. 相似文献
34.
The interfacial tension of aqueous dodecyltrimethylammonium chloride (DTAC) solution/hexane interface has been measured as a function of pressure at concentrations around the critical micelle concentration (CMC). The derivative of the interfacial tension with respect to pressure has been observed to change abruptly at the CMC as in the case of aqueous dodecylammonium chloride (DAC) solution-hexane system studied already. The volume changes associated with the adsorption of DTAC from its monomeric and micellar states have been calculated. The results have indicated that the micelle formation of surfactant is treated like the appearance of a new macroscopic phase in the system. It has also been concluded that the micelle solubilizing hexane bears resemblance to the adsorbed film in terms of the volume. The difference in the pressure dependence of the volume of micelle formation
MW between DTAC and DAC has been attributed to a larger polar group of DTAC. The fact that the value of
MW is larger than that estimated from the conductivity data has been explained by the solubilization of hexane into the micelle. 相似文献
35.
The treatment of octafluorocyclopentene with organolithium reagents gave the corresponding symmetrical disubstituted perfluorocyclopentenes in good to high yields. The reaction with Grignard reagents led to the monosubstituted perfluorocyclopentenes, which were subjected to the further nucleophilic substitution reaction using another Grignard or aryllithium reagents, unsymmetrical disubstituted perfluorocyclopentenes being obtained in high yields. 相似文献
36.
M. Yamanaka Y. Takeda S. Tanigawa A. Nishizawa N. Noda J. Fujita M. Takai M. Shimobayashi Y. Hayashi T. Koizumi K. Nagasaka S. Okajima Y. Tsunawaki A. Nagashima 《International Journal of Infrared and Millimeter Waves》1980,1(1):57-76
A twin optically-pumped far-infrared CH3OH laser has been constructed for use in plasma diagnostics. The antisymmetric doublet due to the Raman-type resonant two-photon transition is reproducibly observed at 118.8 m. With the 118.8-m line, it is obtained from the frequency separation of the anti-symmetric doublet that CH3OH absorption line center is 16±1 MHz higher than the pump 9.7-m P(36) CO2 laser line center. It is shown that the Raman-type resonant two-photon transition is useful in order to get several-MHz phase modulation for the far-infrared laser interferometer. Some preliminary performances of this twin laser for the modulated interferometer are described.This work was carried out under the collaborating research program at the Institute of Plasma Physics, Nagoya University, Nagoya 464, Japan. 相似文献
37.
Inumaru K Kasahara T Yasui M Yamanaka S 《Chemical communications (Cambridge, England)》2005,(16):2131-2133
Well-crystallised TiO2 particles (P-25, 20-30 nm in diameter) were directly incorporated into surfactant-templated mesoporous silica particles (pore diameter: 2.7 nm), and the composite material with a high TiO2 content (60 wt%) showed molecular selective and enhanced photocatalysis for decomposition of 4-nonylphenol. 相似文献
38.
Kobayashi K Yamada Y Yamanaka M Sei Y Yamaguchi K 《Journal of the American Chemical Society》2004,126(43):13896-13897
Selective formation of a homo- or hetero-cavitand cage via metal-coordination, by using tetra(4-pyridyl)-cavitand (1), tetrakis(4-pyridylethynyl)-cavitand (2), or tetrakis(4-cyanophenyl)-cavitand (3) as deep cavitand ligands and Pd(dppp)(OTf)2 (4) as a connector, has been investigated by 1H NMR and CSI-MS. When the cavitand and 4 were mixed in CDCl3 in a 2:4 molar ratio, 1 gave a complicated mixture, whereas 2 or 3 formed a homo-cavitand cage {2(2).4[Pd(dppp)]}8+.8(TfO-) (5) or {2(3).4[Pd(dppp)]}8+.8(TfO-) (6), respectively, as a single species. In a 1:1:4 mixture of 2, 3, and 4, homo-cavitand cages 5 and 6 were observed in a 1:1 ratio. In marked contrast, a mixture of 1, 3, and 4 in a 1:1:4 ratio was exclusively self-assembled into a hetero-cavitand cage {1.3.4[Pd(dppp)]}8+.8(TfO-) (7). The selectivity for the self-assembly of the homo- or hetero-cavitand cage via metal coordination would arise from a combination of factors such as coordination ability and steric demand of cavitand ligands. 相似文献
39.
Aqueous Titanate Sols from Ti Alkoxide-α-Hydroxycarboxylic Acid System and Preparation of Titania Films from the Sols 总被引:1,自引:0,他引:1
Ohya Tomokazu Ito Masamichi Yamada Keiko Ban Takayuki Ohya Yutaka Takahashi Yasutaka 《Journal of Sol-Gel Science and Technology》2004,30(2):71-81
Aqueous titanate sols were prepared by reactions of titanium tetraisopropoxide (TIP) with -hydroxycarboxylic acids in water. IR and Raman spectra, and elemental analyses of the precipitates obtained from the sols revealed that the carboxylates were chelated to titanium but the Ti species were polymerized to form a cluster that had a colloidal nature. Spin-coating of titania (TiO2) thin films from these sols was also examined. Interestingly, it was found that (004) preferentially oriented anatase films with refractive index of 2.54 were obtained from TIP-lactic acid-NH3 (1:1:1, molar ratio) aqueous sol. This crystallographic orientation was characteristic of the TIP-lactic acid-NH3 (1:1:1) system, and was not affected by the kinds of substrates used and the heating rate of the film. TEM observation indicated that small anatase grains had already formed at 200°C. Therefore, the crystallographic orientation might depend strongly on the structure of the chemical species of the precursor solutions. 相似文献
40.
Chiaki Yamanaka Kazuhiko Hashimoto 《Journal of polymer science. Part A, Polymer chemistry》2002,40(23):4158-4166
New polyurethanes with lactone groups in the pendants and main chains were synthesized by the polyaddition of two kinds of L ‐gulonolactone‐derived diols (2,3‐O‐isopropylidene‐L ‐gulono‐1,4‐lactone and 5,6‐O‐isopropylidene‐L ‐gulono‐1,4‐lactone) with hexamethylene diisocyanate and methyl (S)‐2,6‐diisocyanatohexanoate and by the subsequent deprotection of isopropylidene groups. They were hydrolyzed more quickly than the polyurethane derived from methyl β‐D ‐glucofuranosidurono‐6,3‐lactone in a phosphate buffer solution, the pH value of which was 8.0, at 27 °C. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4158–4166, 2002 相似文献