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1.
The initial stage of cubic silicon carbide (3C-SiC) growth on a Si(0 0 1) surface using dimethylsilane (DMS) as a source gas was observed using scanning tunneling microscopy (STM) and reflection high-energy electron diffraction (RHEED). It was found that the dimer vacancies initially existing on the Si(0 0 1)-(2 × 1) surface were repaired by the Si atoms in DMS molecules, during the formation of the c(4 × 4) surface. From the STM measurement, nucleation of SiC was found to start when the Si surface was covered with the c(4 × 4) structure but before the appearance of SiC spots in the RHEED pattern. The growth mechanism of SiC islands was also discussed based on the results of RHEED, STM and temperature-programmed desorption (TPD). 相似文献
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An interesting transformation occurs during acylation of 4(R)-hydroxymethyl-3-methyl-1,3-thiazolidine when 4(R)-acylthiomethyl-3-methyl-1,3-oxazolidines are yielded: the reaction competing with O-acylation is controlled by the bulkiness of the acyl group. 相似文献
4.
T Okuyama M Takata H Nishino A Nishino J Takayasu A Iwashima 《Chemical & pharmaceutical bulletin》1990,38(4):1084-1086
Ninety-five extracts prepared from 14 kinds of Umbelliferous materials were studied to determine their effects on tumor-promoter-induced phenomena in vitro. Of the materials, 5 Chinese crude drugs, two Bai-Hua Qian-Hu classified as Q-I and Q-II types, the root of Peucedanum praeruptorum Dunn., Zi-Hua Qian-Hu, the root of P. decursivum Maxim., Tang-Bai-Zhi, the root of Angelica dahurica Benth, et Hook. var. pai-chi Kimura, Hata et Yen., Dang-Gui, the root of A. acutiloba Kitagawa and 2 Umbelliferous plants, ashita-ba. A. keiskei Koidz., and ama-nyuu, A. edulis Miyabe, showed potent inhibitory effects on 12-O-tetradecanoylphorbol-13-acetate (TPA)-stimulated 32Pi incorporation into phospholipids of cultured cells. From the active fraction of the crude drug "Tang-Bai-Zhi," imperation (1), isoimperatoin (2), oxypeucedanin (3), pabulenol (4), neobyakangelicol (5) and byakangelicin (6) were identified as active or inactive principles. Compound 4 had not previously been isolated from Tang-Bai-Zhi, A. dahurica var. pai-chi. We also discuss the structure-activity relationship among the above 6 kinds of linear-type furanocoumarins, together with 3 kinds of antitumor-promoter coumarins having the same skeleton, psoralen (7), bergapten (8) and xanthotoxin (9), obtained from "ashita-ba" (eaten as a vegetable in Japan). Among the compounds in the present experiment, compounds 1 and 2 showed potent inhibitory activity at the concentration of 50 micrograms/ml and 3-9 were found to have less or no activity. 相似文献
5.
The gas chromatographic separation of 22 carbonyl compounds as their 2,4-dinitrophenylhydrazones was investigated using glass capillary columns. Complete separation of the 2,4-dinitrophenylhydrazones of ten aliphatic aldehydes, eight aliphatic ketones and four aromatic aldehydes was obtained, except for the derivatives of n-valeraldehyde and isobutyl methyl ketone, whose peaks overlapped, and the o- and m-tolualdehyde derivatives, which were poorly separated. The optimum conditions were as follows: stationary phase, SF-96; column size, 20 m × 0.25 mm I.D. ; column temperature, 200-240°; injection and detector temperatures, 280-290°; carrier gas flow-rate, helium 1.0-1.2 ml/min or nitrogen 1.1-1.2 ml/min. The method was applied to the analysis of aliphatic carbonyl compounds in car exhaust fumes and cigarette smoke. 相似文献
6.
Hasegawa JY Takata K Miyahara T Neya S Frisch MJ Nakatsuji H 《The journal of physical chemistry. A》2005,109(14):3187-3200
Excited states of free-base porphyrin isomers, porphycene (Pc), corrphycene (Cor), and hemiporphycene (hPc), were studied by the Symmetry-Adapted Cluster (SAC)/SAC-Configuration Interaction (CI) method. The absorption peaks of the porphyrin isomers were assigned on the basis of the SAC-CI spectra. The X, Y, X', and Y' bands of the porphyrin isomers, which have weak intensities, are identified. The differences in the Q-band absorptions among the isomers were clearly explained by the four-orbital model. In Cor and hPc, the wave function of the B-band corresponds to the mixture of the four-orbital excitations and the optically forbidden excitation of free-base porphin (P), due to the molecular symmetry lowering in the isomers. The B-band character is described by the five-orbital model in Pc and the six-orbital model in Cor and hPc. Two tetrazaporphycenes and two ring-extended (dibenzo) porphycenes were designed, and the Q-band transition moment was successfully controlled. These examples show that the control of the four-orbital energy levels is the guiding principle for pigment design in porphyrin compounds. 相似文献
7.
Matsuda R Kitaura R Kitagawa S Kubota Y Kobayashi TC Horike S Takata M 《Journal of the American Chemical Society》2004,126(43):14063-14070
In situ synchrotron X-ray powder diffraction patterns of porous coordination polymers [[Cu(2)(pzdc)(2)(bpy)].G] have been measured (pzdc = pyrazine-2,3-dicarboxylate, bpy = 4,4'-bipyridine) (where G = H(2)O for CPL-2 superset H(2)()O, G = benzene for CPL-2 superset benzene, and G = void for the apohost). The structures of apohost and CPL-2 superset benzene were determined from Rietveld analysis. Adsorption of benzene in the channels induced a remarkable contraction in the crystal (b axis; 6.8%, volume; 4.9%), although the channels were occupied by the benzene molecules. This crystal transformation provides a new pore structure that is well suited for benzene molecules, and we denote it as a "shape-responsive fitting" transformation. This type of pore gives rise to a new guideline: frameworks can be composed of flexible motifs that are linked via strong bond and/or stiff motifs that are connected via weaker bonds. 相似文献
8.
Ishikawa A Takata T Kondo JN Hara M Kobayashi H Domen K 《Journal of the American Chemical Society》2002,124(45):13547-13553
A Ti-based oxysulfide, Sm(2)Ti(2)S(2)O(5), was studied as a visible light-driven photocatalyst. Under visible light (440 nm < or = lambda < or = 650 nm) irradiation, Sm(2)Ti(2)S(2)O(5) with a band gap of approximately 2 eV evolved H(2) or O(2) from aqueous solutions containing a sacrificial electron donor (Na(2)S-Na(2)SO(3) or methanol) or acceptor (Ag(+)) without any noticeable degradation. This oxysulfide is, therefore, a stable photocatalyst with strong reduction and oxidation abilities under visible-light irradiation. The electronic band structure of Sm(2)Ti(2)S(2)O(5) was calculated using the plane-wave-based density functional theory (DFT) program. It was elucidated that the S3p orbitals constitute the upper part of the valence band and these orbitals make an essential contribution to the small band gap energy. The conduction and valence bands' positions of Sm(2)Ti(2)S(2)O(5) were also determined by electrochemical measurements. It indicated that conduction and valence bands were found to have satisfactory potentials for the reduction of H(+) to H(2) and the oxidation of H(2)O to O(2) at pH = 8. This is consistent with the results of the photocatalytic reactions. 相似文献
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10.
Furusho Y Oku T Hasegawa T Tsuboi A Kihara N Takata T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(12):2895-2903
A dynamic covalent approach to disulfide-containing [2]- and [3]rotaxanes is described. Symmetrical dumbbell-shaped compounds with two secondary ammonium centers and a central located disulfide bond were synthesized as components of rotaxanes. The rotaxanes were synthesized from the dumbbell-shaped compounds and dibenzo-[24]crown-8 (DB24C8) with catalysis by benzenethiol. The yields of isolated rotaxanes reached about 90 % under optimized conditions. A kinetic study on the reaction forming [2]rotaxane 2 a and [3]rotaxane 3 a suggested a plausible reaction mechanism comprising several steps, including 1) initiation, 2) [2]rotaxane formation, and 3) [3]rotaxane formation. The whole reaction was found to be reversible in the presence of thiols, and thermodynamic control over product distribution was thus possible by varying the temperature, solvent, initial ratio of substrates, and concentration. The steric bulk of the end-capping groups had almost no influence on rotaxane yields, but the structure of the thiol was crucial for reaction rates. Amines and phosphines were also effective as catalysts. The structural characterization of the rotaxanes included an X-ray crystallographic study on [3]rotaxane 3 a. 相似文献