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21.
A general synthetic scheme for tamoxifen-type tetrasubstituted olefins based on the novel Cu-catalyzed carbomagnesation across alkynyl(2-pyridyl)silane has been developed. A wide array of electronically and structurally diverse tetrasubstituted olefins can be prepared in a regiocontrolled, stereocontrolled, and diversity-oriented manner. Noteworthy features are that (i) the three aryl groups, which are believed to be important (essential) for anti-estrogenic activity, can be varied at will because they all stem from readily available aryl iodides, and (ii) any stereo- and regioisomers can, in principle, be prepared by simply changing the applying order of aryl iodides into the sequence. 相似文献
22.
The characteristic fragment ions and visualization of cationic starches on pulp fiber using ToF‐SIMS
Yasuyuki Matsushita Takuya Sekiguchi Kaori Saito Toshiyuki Kato Takanori Imai Kazuhiko Fukushima 《Surface and interface analysis : SIA》2007,39(6):501-505
Time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) was used to investigate the distribution of cationic starch on pulp fiber. To identify the characteristic fragment ions of the cationic starches, deuterium‐labeled cationic starches were prepared and analyzed using ToF‐SIMS. The starch 2‐hydroxypropyltrimethylammonium chloride derivative generated characteristic fragments at m/z 58 and 59, which were identified as [H2C?N(CH3)2]+ and [N(CH3)3]+·, respectively. The fragmentation patterns were also suggested. From the imaging analysis, the adsorption of the cationic starch on fibers was uneven on individual fibers, as well as between fibers. This may have been on account of fiber morphology and structure. On examining scanning electron microscope (SEM) images, the quaternary ammonium starch derivative (QS) did not penetrate the fiber. No migration of cationic starch was observed under various drying conditions. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
23.
Toshiyuki Uryu Toshiyuki Seki Tokiji Kawamura Akashi Funamoto Kei Matsuzaki 《Journal of polymer science. Part A, Polymer chemistry》1976,14(12):3035-3044
The stereoregularity of polystyrene prepared by anionic polymerization was determined by means of 13C-NMR spectroscopy. The stereoregularity changed with such polymerization conditions as catalyst, solvent, and temperature. Sodium naphthalene as catalyst gave a syndiotactic-rich polystyrene of 66–68% syndiotactic dyads independently of solvent and temperature, while potassium and cesium naphthalenes as catalyst produced polystyrenes with different stereoregularities ranging from syndiotactic-rich to isotactic-rich configurations, depending on solvent and temperature. The mechanism of anionic polymerization which caused the difference in stereoregularity was discussed from the viewpoint of growing ionic species. 相似文献
24.
Toshiyuki Chikuma Yoko ShimabukuroTakeya Iguchi Akira TanakaKyoji Taguchi Takeshi KatoMitsune Yamaguchi Hiroshi Hojo 《Analytica chimica acta》2002,457(2):157-164
A rapid and sensitive assay for the determination of Dns-His-Lys-Arg-His-Lys cleaving enzyme activity is reported. This assay is based on fluorimetric detection of a dansylated dipeptide, 5-dimethylaminonaphthalene-1-sulfonyl-His-Lys, enzymatically formed from the substrate 5-dimethylaminonaphthalene-1-sulfonyl-His-Lys-Arg-His-d-Lys, after separation by high-performance liquid chromatography (HPLC) using a C-18 reversed-phase column by isocratic elution. This assay is sensitive enough to measure 5-dimethylaminonaphthalene-1-sulfonyl-His-Lys at concentrations as low as 7 pmol, and yields highly reproducible results and requires less than 9.0 min per sample for separation and quantitation. The optimum pH for Dns-His-Lys-Arg-His-Lys cleaving enzyme activity was 7.5-8.0. The Michaelis constant (Km) and the maximum velocity (Vmax) values were 33.3 μM and 47.07 pmol/(μg h), respectively with the use of enzyme extract obtained from bovine pituitary. By using this assay, axonal transport of this enzyme activity was observed 48 h after double ligations of rat sciatic nerves. The high sensitivity and selectivity of this assay would be useful for clarification of the physiological role of this enzyme. 相似文献
25.
[reaction: see text] We have developed an efficient copper-catalyzed allylation of carbonyl derivatives using allyl(2-pyridyl)silanes, in which the strong directing effect of the 2-pyridyl group was observed. A useful synthesis and allylation of substituted allyl(2-pyridyl)silanes is also described. 相似文献
26.
Jin-Ming Lin Tatsuro Nakagama Hitoshi Okazawa Xing-Zheng Wu Toshiyuki Hobo 《Fresenius' Journal of Analytical Chemistry》1996,354(4):451-454
Capillary gel electrophoresis (CGE) was successfully applied to the separation of optically active isomers and position isomers by incorporating a suitable cyclodextrin chiral selector in polyacrylamide gel. A commercially available ß-cyclodextrin (ß-CD) was used for enantioselectivity towards o-, m- and p-nitrobenzoic acid, o-, m- and p-hydroxybenzoic acid, o-, m- and p-toluic acid and the optical isomers of dansyl-D,L-leucine and R,S-1,1-binaphthyl-2,2-dihydrogenphosphate. Especially the effect of organic solvents, such as acetonitrile, methanol, dimethylsulphoxide and others were examined in detail. The resolution varied to some extent with the addition of the organic solvent to the polyacrylamide gel and the running buffer solution. The possible mechanism has also been discussed. In addition, quantitative aspects of the separation of stereoisomers using CGE have been studied, showing that both the resolution and accuracy of the determinations were affected by the ratio of the enantiomers. 相似文献
27.
Hamada T Matsunaga S Yano G Fusetani N 《Journal of the American Chemical Society》2005,127(1):110-118
Polytheonamides A and B are highly cytotoxic polypeptides with 48 amino acid residues isolated from the marine sponge, Theonella swinhoei. The structure of polytheonamide B was determined by spectral and chemical methods, especially extensive 2D NMR experiments, which resulted in the unprecedented polypeptide structure; the N-terminal glycine blocked with a 5,5-dimethyl-2-oxo-hexanoyl group, the presence of eight tert-leucine, three beta-hydroxyvaline, six gamma-N-methylasparagine, two gamma-N-methyl-beta-hydroxyasparagine, and beta,beta-dimethymethionine sulfoxide residues. More significantly, it has the sequence of alternating D- and L-amino acids. Polytheonamide A is an epimer of polytheonamide B differing only in the stereochemistry of the sulfoxide of the 44(th) residue. 相似文献
28.
Toshiyuki Yamashita Takeo Fujino Norio Masaki Hiroaki Tagawa 《Journal of solid state chemistry》1981,37(2):133-139
The structural parameters of α- and β-CdUO4 crystals are determined by X-ray powder diffraction technique. α-CdUO4 is rhombohedral and cell parameters are a = 6.233(3) Å and α = 36.12(5)°. β-CdUO4 crystallizes in a C-centered orthorhombic cell with a = 7.023(4), b = 6.849(3), c = 3.514 (2) Å. The space groups are for α-CdUO4 and Cmmm for β-CdUO4. α-CdUO4: 1U in (000), 1Cd in (), 2O(1) in ±(uuu), 2O(2) in ±(vvv); u = 0.113, v = 0.350, Z = 1. β-CdUO4: 2U in (), 2Cd in (), 4O(1) in (), 4O(2) in (); x = 0.159, y = 0.278, Z = 2. β-CdUO4 contains collinear uranyl UO2+2 groups with a UO(1) distance of 1.91 Å, located either along or parallel to the c axis whereas the UO(1) bond length in α-CdUO4 is 1.98 Å which is longer than the usual uranyl bond length. 相似文献
29.
Miura T Goto K Waragai H Matsumoto H Hirose Y Ohmae M Ishida HK Satoh A Inazu T 《The Journal of organic chemistry》2004,69(16):5348-5353
The Bfp-OH, a novel fluorous protecting reagent, was able to be easily prepared. The Bfp group was readily introduced to a carbohydrate, removed in high yield, and recyclable after cleavage. The use of the Bfp group made it possible to synthesize a pentasaccharide by minimal column chromatography purification. Each synthetic intermediate was able to be easily purified only by simple fluorous-organic solvent extraction and monitored by TLC, NMR, and MS. 相似文献
30.
The leaching behavior of two different residual oils is investigated with 24 organic solvents including alkanes, aromatics, esters, ethers ketones, alcohols and nitrogen compounds. A 2-g portion of sample oil is shaken with 20 ml of the organic solvent. The leaching of the organic matrix of the oil is determined by weighing the dissolved organic matrix after removal of solvent. The leaching of vanadium, iron and nickel was determined by flame atomic absorption spectrophotometry after ashing of the dissolved fraction. The leaching of those metals depends strongly on the solvent used; for example, vanadine is almost completely leached into toluene, but only slightly into methanol. The leaching of iron is poor compared with that of vanadium or nickel. In most solvents, leaching of those metal-containing species is poorer than that of organic material. Exceptionally, N,N-dimethylformamide is more efficient in leaching vanadium species than organic material. 相似文献