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11.
Tomoyuki Yoshimura 《Tetrahedron letters》2004,45(50):9241-9244
Diastereoselective construction of the 19-epi-C18-C25 segment of (−)-lasonolide A was achieved using a 5-exo-trigonal mode of radical cyclization for the creation of the contiguous quaternary and tertiary stereogenic centers at C22 and C23 as the key reaction step. During the dehydration stage, it was found that an unusual inversion of configuration took place. 相似文献
12.
In a rubidium manganese hexacyanoferrate, RbMn[Fe(CN)(6)], the magnetic susceptibility (chi(M)) decreased at 225 K (=T(1/2)decreasing) and abruptly increased at 300 K (=T(1/2)increasing) in the cooling and warming processes, respectively. X-ray photoelectron spectroscopy and infrared spectroscopy indicated that the high-temperature (HT) and low-temperature (LT) phases were composed of Mn(II)-NC-Fe(III) and Mn(III)-NC-Fe(II), respectively. A structural change from cubic (F43m, a = 10.533 A) to tetragonal (I4m2, a = b = 7.090 A, c = 10.520 A) accompanied the phase transition, and, on the basis of these results, the HT and LT phases were assigned to Mn(II)(t(2g)(3)e(g)(2), (6)A(1g); S = (5)/(2))-NC-Fe(III) (t(2g)(5), (2)T(2g); S = (1)/(2)) and Mn(III)(e(g)(2)b(2g)(1)a(1g)(1), (5)B(1g); S = 2)-NC-Fe(II) (b(2g)(2)e(g)(4), (1)A(1g); S = 0), respectively. This phenomenon is caused by a metal-to-metal charge transfer from Mn(II) to Fe(III) and a Jahn-Teller distortion of the produced Mn(III) ion. The reaction mechanism is discussed, considering the entropy difference between the HT and LT phases. 相似文献
13.
The reaction of zirconium n-propoxide in glycol at 300°C yielded microcrystalline tetragonal zirconia (ZrO2). The crystallite size of the product depended on the carbon number of the glycol and increased in the following order (carbon
number of glycol): 2<6<4, which suggested that the heterolytic cleavage of O-C bond of gylcoxide formed by transesterification
is the prime factor for the formation of the product. In toluene, zirconium isopropoxide also gave tetragonal zirconia at
300°C, and zirconium tert-butoxide decomposed at 200°C yielding amorphous zirconia, while zirconium n-propoxide was stable at 300°C. These results suggest that the reaction in toluene depends on the structure of the alkyl group
of the alkoxides. Thus-obtained tetragonal zirconias maintained large surface areas (90–160 m2/g) even after calcination at 500°C. 相似文献
14.
Two-dimensional network formation of cardiac myocytes in agar microculture chip with 1480 nm infrared laser photo-thermal etching 总被引:1,自引:0,他引:1
We have developed a new method that enables agar microstructures to be used to cultivate cells and that allows cell network patterns to be controlled. The method makes use of non-contact three-dimensional photo-thermal etching with a 1480 nm infrared focused laser beam, which is strongly absorbed by water and agar gel, to form the shapes of agar microstructures. It allows microstructures to be easily formed in an agar layer within a few minutes, with cell-culture holes formed by the spot heating of a 100 mW laser and tunnels by the tracing of a 100 microm s(-1), 40 mW laser. We cultivated rat cardiac myocytes in adjacent microstructures and observed synchronized beating in them 90 min after they had made physical contact. Our results indicate that the system can make and use microstructures for cell-network cultivation in a minimal amount of time without any expensive microfabrication facilities or complicated procedures. 相似文献
15.
Hiroshi Narita Tomoyuki Okimoto Seishi Machida 《Journal of polymer science. Part A, Polymer chemistry》1970,8(10):2725-2731
Polymerization of acrylamide initiated with a pinacol–ceric ion redox system was investigated. The polymer obtained was found to contain one cerium atom in a polymer molecule. It was considered that the cerium atom was introduced into the polymer molecule by the termination reaction as there is no cerium atom in the initiating radical in the present system. A similar termination reaction was attained by ferric ion but not by cerous ion. The metal ion was considered to terminate the polymerization to form a stable polymer. Some considerations on the structure of the reaction product relating to the polymerization mechanism were discussed. 相似文献
16.
Okihiro Sugihara Tomoyuki Hirama Hisashi Fujimura Naomichi Okamoto 《Optical Review》1996,3(3):150-152
Thin film waveguides of germanosilicate glass are fabricated byrf-sputtering. Second-order nonlinearity ofd 33=3.2 pm/V is obtained from electrically poled film, and the lifetime of the nonlinearity is found to be310 years. The poled channel-waveguide is prepared and the Cerenkov-type phase-matched frequency doubling is successfully observed. 相似文献
17.
Michiko Iwamura Yuka Gotoh Tomoyuki Hashimoto Reiko Sakurai 《Tetrahedron letters》2005,46(37):6275-6277
Michael addition reactions of acetoacetates and malonates with acrylates in a 5 M KOH aqueous solution without using any other catalysts are described. When they are either tert-butyl or benzyl esters, the reaction proceeded very rapidly to afford moderate to high yields of the corresponding bis-Michael adducts that are unexpectedly stable under these conditions. 相似文献
18.
Koga T Taguchi K Kinoshita T Higuchi M 《Chemical communications (Cambridge, England)》2002,(3):242-243
A novel artificial protein with simple primary structure, poly(gamma-methyl-L-glutamate)-grafted polyallylamine, has been prepared and the resultant peptide has shown a unique property of pH-regulated conformation and morphology. 相似文献
19.
Tomoyuki Esumi 《Tetrahedron letters》2004,45(37):6941-6945
Isoplagiochin D, a highly strained macrocyclic bis(bibenzyls) with two biaryl units isolated from the liverwort Pladiochila fruticosa, was prepared in 10.6% overall yield for the 11 steps by an efficient synthetic approach involving the construction of two bibenzyl and one biaryl units using Horner-Wadsworth-Emmons and Suzuki-Miyaura protocols. 相似文献
20.
Octadecapeptides carrying a ferrocene moiety at the molecular terminal were self-assembled on gold, and long-range electron transfer from the ferrocene moiety to gold was investigated by electrochemical methods. Effects on electron transfer of dipole moment of helical peptides, linkers connecting the peptide to gold, and chromophores introduced into the side chains were discussed. Cyclic voltammetry of the monolayers in an aqueous solution revealed that long-range electron transfer over 40 A occurred along the peptide molecule. Chronoamperometry showed that the long-range electron transfer should be ascribed to a hopping mechanism with use of amide groups as hopping sites. Electron transfer through the long peptide was not significantly accelerated by the dipole moment. However, the linker remarkably affected electron transfer depending on whether it was a methylene chain or a phenylene group, suggesting that local electron transfer between gold and the peptides should be the slowest step to determine the overall rate. Pyrenyl groups introduced into the side chains in the middle of the peptide molecule did not noticeably change electron transfer, probably because pyrenyl groups were too distant to allow direct electron transfer between them. Electrostatic potential profiles across the peptide monolayers were also calculated to explain reasonably the several interesting features in the present peptide systems. 相似文献