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61.
T. Nagai K. Sakai T. Asaka A. Yamazaki Y. Matsui 《Journal of solid state chemistry》2006,179(6):1898-1903
The crystal structure of our newly discovered Sr-Co-O phase is investigated in detail through high-resolution electron microscopy (HREM) techniques. Electron diffraction (ED) measurement together with energy dispersive X-ray spectroscopy (EDS) analysis show that an ampoule-synthesized sample contains an unknown Sr-Co-O ternary phase with monoclinic symmetry and the cation ratio of Sr/Co=1. From HREM images a layered structure with a regular stacking of a CdI2-type CoO2 sheet and a rock-salt-type Sr2O2 double-layered block is observed, which confirms that the phase is the parent of the more complex “misfit-layered (ML)” cobalt oxides of [MmA2Om+2]qCoO2 with the formula of [Sr2O2]qCoO2, i.e. m=0. It is revealed that the misfit parameter q is 0.5, i.e. the two sublattices of the CoO2 sheet and the Sr2O2 block coexist to form a commensurate composite structure. We propose a structural model with monoclinic P21/m symmetry, which is supported by simulations of ED patterns and HREM images based on dynamical diffraction theory. 相似文献
62.
Horio T Yamazaki M Maeda S Hatamoto T Kishimoto N Ohno K 《The Journal of chemical physics》2005,123(19):194308
A low-temperature discharge nozzle source with a liquid-N(2) circulator for He*(2(3)S) metastable atoms has been developed in order to obtain the state-resolved collision energy dependence of Penning ionization cross sections in a low collision energy range from 20 to 80 meV. By controlling the discharge condition, we have made it possible to measure the collision energy dependence of partial ionization cross sections (CEDPICS) for a well-studied system of CH(3)CN+He*(2(3)S) in a wide energy range from 20 to 350 meV. The anisotropic interaction potential energy surface for the present system was obtained starting from an ab initio model potential via an optimization procedure based on classical trajectory calculations for the observed CEDPICS. A dominant attractive well depth was found to be 423 meV (ca. 10 kcal/mol) at a distance of 3.20 A from the center of mass of CH(3)CN in the N-atom side along the CCN axis. In addition, a weak attractive well (ca. 0.9 kcal/mol) surrounding the methyl group (-CH(3)) has been found and ascribed to the interaction between an unoccupied molecular orbital of CH(3)CN and 2s atomic orbital of He*(2(3)S). 相似文献
63.
Munakata R Katakai H Ueki T Kurosaka J Takao K Tadano K 《Journal of the American Chemical Society》2003,125(48):14722-14723
The first total synthesis of (+)-macquarimicin A (1), a novel inhibitor of neutral sphingomyelinase (N-SMase) with antiinflammatory activity, has been accomplished. The present work determined the absolute configuration of (+)-1 and revised the C(2)-C(3) geometry to be Z. The synthesis features a transannular Diels-Alder reaction, which constructed the tetracyclic framework stereoselectively, and a convergent and efficient synthetic pathway, which afforded (+)-macquarimicin A (1) in 27 steps (longest linear sequence) with 9.9% overall yield. 相似文献
64.
[reaction: see text] Phosphates from 3-substituted 4,4,4-trifluorobut-2-en-1-ols were found to be effective for construction of CF3-containing quaternary carbon centers by way of Cu(I)-catalyzed Grignard reactions in the presence of catalytic amounts of CuCN and trimethylsilyl chloride (TMSCl) in an anti S(N)2' manner. 相似文献
65.
Lewis acid and substituent dependency on the regioselectivity of hydrosilylation of propiolate esters 1a-c with tris(trimethylsilyl)silane (2a) was found. The reaction of methyl and ethyl propiolate esters and 2a without Lewis acid and in the presence of EtAlCl2 and Et2AlCl gave beta-silicon-substituted Z-alkenes 3 selectively. On the other hand, reaction in the presence of AlCl3 in dichloromethane gave alpha-silicon-substituted alkenes 4. In the case of trifluoroethyl propiolate ester 1c, reaction with aluminum chloride-based Lewis acids gave alpha-silicon-substituted alkenes 4 exclusively. Two competitive mechanisms, free-radical and ionic, are proposed as the source of the complementary regioselectivity displayed in these reactions. A transition state of the radical-forming step was obtained computationally. The reaction of various reactive acetylene substrates and 2a without Lewis acid and without solvent at room temperature gave beta-silicon-substituted Z-alkenes 3 selectively. 相似文献
66.
T. Yamazaki 《Zeitschrift für Physik A Hadrons and Nuclei》1992,341(2):223-225
A new way to promote antihydrogen formation via the recently discovered long-lived metastable states of antiprotonic helium atoms is discussed. Recombination processes such ase
–
¯pHe++ +e
+
e
– e
+
¯p + He0 are possible in this respect.Dedicated to Prof. Dr. P. Kienle on the occasion of his 60th birthday 相似文献
67.
Y. Saito-Kokubu K. Yasuda M. Magara Y. Miyamoto S. Sakurai S. Usuda H. Yamazaki S. Yoshikawa 《Journal of Radioanalytical and Nuclear Chemistry》2007,273(1):183-186
In order to know the distribution of plutonium derived from the Nagasaki atomic bomb, soil samples were measured to determine
the 240Pu/239Pu isotope ratio of and concentrations of 239+240Pu and 137Cs. The 239+240Pu concentrations in soils, except for Nishiyama area, were close to the average concentration of soil collected in Japan.
In soils collected at the Nishiyama area and at the eastern area of Nagasaki Prefecture and at part of northern area in Kumamoto
Prefecture, the 240Pu/239Pu ratios were lower than the global fallout values. This suggests that plutonium from the atomic bomb was deposited in the
eastern area from the hypocenter reaching up to 100 km eastwards. 相似文献
68.
Unsaturated transition metal carbonyls are important in processes such as organometallic synthesis, homogeneous catalysis, and photochemical decomposition of organometallics. In particular, a metal monocarbonyl offers a zeroth-order model for interpreting the chemisorption of a CO molecule on a metal surface in catalytic activation processes. Quite large numbers of theoretical papers have appeared which predict spectroscopic and structural properties of transition metal carbonyls. The nickel monocarbonyl NiCO has been one of the metal carbonyls most extensively studied by the theoretical calculations. At least 50 theoretical studies have been published on this simplest transition metal carbonyl up to the present time. However, experimental evidence of NiCO is much more sparse than theoretical predictions, and the actual structure of NiCO has never been determined by any experimental methods. This Communication reports the first preparation of free nickel monocarbonyl and observation of its rotational transitions. The NiCO molecule was generated by the sputtering reaction of a Ni cathode in the presence of CO. The accurate bond lengths of Ni-C and C-O were experimentally determined from isotopic data and were compared with the theoretical predictions for the first time. 相似文献
69.
Y. Yamazaki H. Kataoka A. Miyazakl M. Watanabe T. Ootakl 《Photochemistry and photobiology》1996,64(2):387-392
The sexual development of the fungus Phycomyces is inhibited by light. The action spectra for this photoinhibitory effect were determined for 48 h continuous exposure between 350 and 700 nm wavelengths during the mating process. Effective wavelengths were shorter than 490 nm, but the most effective wavelengths depended on the stage of sexual development. In early stages of progametangium formation, the major peaks appeared near 360 nm with small shoulders at 410 nm, but in later stages, after gametangium formation, only single peaks were detected in the UVA range (350–390 nm). Low-fluence irradiation in the later stage, however, revealed inhibitory effectiveness at 370–410 nm, implying the existence of a dual photoresponse and multiple regulatiory systems in the mating process of Phycomyces. 相似文献
70.
The potential energy surface of benzene (C(6)H(6)) with a He*(2(3)S) atom was obtained by comparison of experimental data in collision-energy-resolved two-dimensional Penning ionization electron spectroscopy with classical trajectory calculations. The ab initio model interaction potentials for C(6)H(6)+He*(2(3)S) were successfully optimized by the overlap expansion method; the model potentials were effectively modified by correction terms proportional to the overlap integrals between orbitals of the interacting system, C(6)H(6) and He*(2(3)S). Classical trajectory calculations with optimized potentials gave excellent agreement with the observed collision-energy dependence of partial ionization cross sections. Important contributions to corrections were found to be due to interactions between unoccupied molecular orbitals and the He*2s orbital. A C(6)H(6) molecule attracts a He*(2(3)S) atom widely at the region where pi electrons distribute, and the interaction of -80 meV (ca. -1.8 kcal/mol) just cover the carbon hexagon. The binding energy of a C(6)H(6) molecule and a He* atom was 107 meV at a distance of 2.40 A on the sixfold axis from the center of a C(6)H(6) molecule, which is similar to that of C(6)H(6)+Li and is much larger than those of the C(6)H(6)+[He,Ne,Ar] systems. 相似文献