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21.
A method of free energy calculation is proposed, which enables to cover a wide range of pressure and temperature. The free energies of proton-disordered hexagonal ice (ice Ih) and liquid water are calculated for the TIP4P [J. Chem. Phys. 79, 926 (1983)] model and the TIP5P [J. Chem. Phys. 112, 8910 (2000)] model. From the calculated free energy curves, we determine the melting point of the proton-disordered hexagonal ice at 0.1 MPa (atmospheric pressure), 50 MPa, 100 MPa, and 200 MPa. The melting temperatures at atmospheric pressure for the TIP4P ice and the TIP5P ice are found to be about T(m)=229 K and T(m)=268 K, respectively. The melting temperatures decrease as the pressure is increased, a feature consistent with the pressure dependence of the melting point for realistic proton-disordered hexagonal ice. We also calculate the thermal expansivity of the model ices. Negative thermal expansivity is observed at the low temperature region for the TIP4P ice, but not for the TIP5P ice at the ambient pressure. 相似文献
22.
Gas mixtures of methane and ethane form structure II clathrate hydrates despite the fact that each of pure methane and pure ethane gases forms the structure I hydrate. Optimization of the interaction potential parameters for methane and ethane is attempted so as to reproduce the dissociation pressures of each simple hydrate containing either methane or ethane alone. An account for the structural transitions between type I and type II hydrates upon changing the mole fraction of the gas mixture is given on the basis of the van der Waals and Platteeuw theory with these optimized potentials. Cage occupancies of the two kinds of hydrates are also calculated as functions of the mole fraction at the dissociation pressure and at a fixed pressure well above the dissociation pressure. 相似文献
23.
Yoshiyuki Koyama Kazunari Harima Kei Matsuzaki Toshiyuki Uryu 《Journal of polymer science. Part A, Polymer chemistry》1985,23(12):2989-2998
1,4-Anhydro-2,3-di-O-benzyl-α-L -arabinopyranose (=1,5-anhydro-2,3-di-O-benzyl-β-L -arabinofuranose) (ABAP) was synthesized and underwent cationic ring-opening polymerization with several kinds of Lewis acids. All the polylmers prepared by Lewis acids as catalyst were found to consist of two different structural units, α-furanosidic and β-furanosidic units, and the structure of the polymers greatly depended on the polymerization conditions. Polymerization of ABAP with antimony pentachloride catalyst at 0°C for 42 h gave a polymer with the highest α content of 93%, and that at ?20°C for 3 h gave a polymer with the lowest (25%) α content. The other catalysts such as phosphorus pentafluoride, boron trifluoride etherate, niobium pentafluoride, and tantalum pentafluoride also afforded polymers with mixed structure of α-and β-furanosides. After debenzylation of poly(ABAP), a new polysaccharide, L -arabinofuranan was obtained. 相似文献
24.
Koichiro Koyama Yusuke Hirasawa Tomohiro Hoshino Norimichi Nakahata 《Tetrahedron》2005,61(15):3681-3690
Seven new Lycopodium alkaloids, lannotinidines A-G (1-7), have been isolated from the club moss Lycopodium annotinum and L. annotinum var. acrifolium. Stereochemistry of 1-7 was elucidated by combination of NOESY correlations and chemical transformation. Lannotinidines B-E (2-5) elevated NGF mRNA expression. 相似文献
25.
Ikuo Ashikawa Mariko Kito Kimiyuki Satoh Hiroyuki Koike Yorinao Inoue Kayoko Saiki Kiyoshi Tsukida Yasushi Koyama 《Photochemistry and photobiology》1987,46(2):269-275
All- trans β-carotene-5,6-epoxide has been found in the thylakoid membranes of spinach and of the cyanobacterium Synechococcus vulcanus Copeland. The epoxide was extracted from the thylakoid membranes with acetone, and was isolated by high-performance liquid chromatography (HPLC). The structure of the epoxide was identified by means of mass, Raman, and electronic absorption spectroscopy. Changes in the amount of the epoxide, as a result of epoxidation and (apparent) de-epoxidation reactions in the membranes, were traced by analysis of extracts on HPLC. In isolated thylakoid membranes, only the epoxidation reaction took place. The reaction was caused by irradiation or by the addition of ferricyanide, suggesting that electron transport reactions in the membranes are involved in the epoxidation. In intact spinach leaves, however, both epoxidation and de-epoxidation took place; the extent of epoxidation correlated with the intensity of light incident on the leaves. The epoxidation and de-epoxidation of all- trans β-carotene are contrasted with those of xanthophylls (in the violaxanthin cycle). 相似文献
26.
Anyun Zhang Yuezhou Wei Harutaka Hoshi Mikio Kumagai Masayoshi Kamiya Tomozo Koyama 《Radiation Physics and Chemistry》2005,72(6):669-678
The resistance of a novel silica-based N,N,N′,N′-tetraoctyl-3-oxapentane-1,5-diamide (TODGA) polymeric adsorption material (TODGA/SiO2-P) against nitric acid, temperature and γ-irradiation had been investigated. The adsorption property of the treated TODGA/SiO2-P was evaluated by a 3 M HNO3 solution containing 0.01 M Nd(III). It was found that both 3 and 0.01 M HNO3 concentrations did not decrease the stability of TODGA/SiO2-P at 25°C. The quantity of TODGA leaked from TODGA/SiO2-P was equivalent to its solubility in the corresponding HNO3 aqueous solution. The effect of 3 M HNO3 on the leakage of TODGA at 80°C was significantly higher than that in 0.01 M HNO3 as well as in all cases at 25°C. The amount of Nd(III) adsorbed towards the treated TODGA/SiO2-P was determined in the range of 0.143–0.148 mmol/g for the HNO3 concentration effect and 0.142–0.0506 mmol/g for the temperature effect. γ-Irradiation showed a more noticeable destruction effect on TODGA/SiO2-P. The content of TODGA leaked increased with an increase in the γ-irradiation dose (ID) from 1.06 to 3.72 MGy in terms of the linear equation [TODGA]=794.5ID+84.0. The amount of Nd(III) adsorbed onto the irradiated TODGA/SiO2-P decreased rapidly from 0.134 to 0.0438 mmol/g, which was lower than 0.153 mmol/g, the adsorption of fresh TODGA/SiO2-P for Nd(III), according to the equation QNd(III)=−0.0301ID+0.160, showing that a large quantity of TODGA leaked from TODGA/SiO2-P. The adsorbed amount of Nd(III) decreased obviously in this order: the HNO3 concentration effect, temperature effect and γ-irradiation. 相似文献
27.
Kohara T Koyama T Fujimura M Tanaka H Maeda J Fujimoto T Yamamoto I Arita M 《Chemical & pharmaceutical bulletin》2002,50(6):818-821
The oxidation behavior of Y-931, a potent atypical antipsychotic drug, was compared with that of clozapine and olanzapine. In two enzymatic systems (horseradish peroxidase (HRP)/glutathione (GSH) and HRP/H(2)O(2)/GSH) which generate thiyl radicals, clozapine markedly strengthened the electron paramagnetic resonance (EPR) signal for the radical. Olanzapine, Y-931 and the major metabolites (compounds 1-3) had no or minimal effect on the intensity of this signal. In addition, the redox potential values for the three derivatives were in accord with the EPR spin trapping results. In toxicological experiments in human leukocytes, a concentration-dependent toxicity was observed when neutrophils were incubated with clozapine (1-10 micromol/l) and H(2)O(2) (1 mmol/l). However, Y-931 and olanzapine did not show remarkable toxicity under the conditions. 相似文献
28.
This paper shares results from a secondary analysis of data from the participation of Japanese, Singaporean, and U.S. students in the International Project on Mathematical Attainment (IPMA). IPMA was a longitudinal study to assess the mathematics achievement of primary students from their first year of schooling through the end of fifth grade. Tests were constructed to enable achievement on the same items to be assessed over multiple years, thus permitting the assessment of growth in achievement throughout primary school. Achievement is compared to the grade at which the content is introduced so that achievement can be related to students’ opportunity to learn. 相似文献
29.
Kazuo Koyama Takashi Hirao Akira Toriba Kazuichi Hayakawa 《Biomedical chromatography : BMC》2013,27(5):583-588
The quality of starch‐containing foods may be significantly impaired by contamination with very small amounts of α‐amylase, which can enzymatically hydrolyze the starch and cause viscosity loss. Thus, for quality control, it is necessary to have an analytical method that can measure low amylase activity. We developed a sensitive analytical method for measuring the activity of α‐amylase (from Bacillus subtilis) in starch‐containing foods. The method consists of six steps: (1) crude extraction of α‐amylase by centrifugation and filtration; (2) α‐amylase purification by desalting and anion‐exchange chromatography; (3) reaction of the purified amylase with boron‐dipyrromethene (BODIPY)‐labeled substrate, which releases a fluorescent fragment upon digestion of the substrate, thus avoiding interference from starch derivatives in the sample; (4) stopping the reaction with acetonitrile; (5) reversed‐phase solid‐phase extraction of the fluorescent substrate to remove contaminating dye and impurities; and (6) separation and measurement of BODIPY fluorescence by HPLC. The proposed method could quantify α‐amylase activities as low as 10 mU/mL, which is enough to reduce the viscosity of starch‐containing foods. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
30.