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31.
1-Alkoxy-3-trimethylsilylmethyl- and 1-alkoxy-3-trimethylsilyl-l,3-butadienes () were newly prepared. The cycloaddition reactions of with various dienophiles including heterodienophiles were found to proceed very smoothly in a perfectly regiospecific mode. 相似文献
32.
Ray K Nakahara H Sakamoto A 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(1-2):103-107
The fluorescence lifetimes decays and picosecond time-resolved fluorescence spectra were measured to investigate the dynamics of the excited state of sulforhodamine B (SRB) molecules adsorbed in the mono- and multilayered Langmuir-Blodgett (LB) films of octadecylamine. Steady-state and time-resolved fluorescence spectroscopy reveals that the fluorescence lifetimes and contents of the monomer and dimers in the molecular organizates depend upon the concentration of the dye in the solution and the adsorption process. SRB dye molecules adsorbed in LB films have been imaged with scanning near-field optical microscopy (SNOM). This information is exploited to map the distribution with molecular spatial resolution. SNOM provide the visual evidence of the monomers and dimers of SRB in cationic LB films. 相似文献
33.
34.
Masatoshi Oue Akira Ishigaki Keiichi Kimura Yousuke Matsui Toshiyuki Shono 《Journal of polymer science. Part A, Polymer chemistry》1985,23(7):2033-2042
Poly- and bis(thiacrown ether) derivatives in which some oxygen atoms of benzocrown ether moiety are replaced by sulfur atoms have been synthesized. Their cation-binding abilities were investigated by using the solvent extraction method. The poly- and bis(benzothiacrown ether)s showed great affinity for silver ion, being more excellent in the affinity than the corresponding monocyclic analogs. They, however, possess very poor cation-binding ability for alkali and alkaline-earth metal ions. The poly- and bis(thiacrown ether)s also bind mercuric ions effectively, whereas the corresponding monomeric analogs do not at all. 相似文献
35.
Yoshihiro Itoh Masamitsu Inoue Tomoko Takahashi Akira Hachimori Satoshi Suzuki 《Journal of polymer science. Part A, Polymer chemistry》1995,33(7):1069-1074
Alternating and random copolymers of 9-phenanthrylmethyl methacrylate or 2-(9-carbazolyl)ethyl methacrylate with styrene were synthesized and their fluorescence properties were examined. There was no noticeable difference in the spectral features of the alternating and random copolymers in tetrahydrofuran (THF), demonstrating that this type of polymers have no quenching sites in the polymer chains. The fluorescence quenching studies indicated that the alternating copolymers permitted singlet-state energy migration as efficiently as the corresponding random copolymers but less efficiently than the random copolymers with higher chromophore contents. These results strongly suggest that to be chromophores close to each other is most important for facilitation of an intramolecular energy migration. © 1995 John Wiley & Sons, Inc. 相似文献
36.
Yoshihiko Nishimori Katsuhiko Kanaizuka Dr. Masaki Murata Dr. Hiroshi Nishihara Prof. 《化学:亚洲杂志》2007,2(3):367-376
Films of linear and branched oligomer wires of Fe(tpy)2 (tpy=2,2′:6′,2′′‐terpyridine) were constructed on a gold‐electrode surface by the interfacial stepwise coordination method, in which a surface‐anchoring ligand, (tpy? C6H4N?NC6H4? S)2 ( 1 ), two bridging ligands, 1,4‐(tpy)2C6H4 ( 3 ) and 1,3,5‐(C?C? tpy)3C6H3 ( 4 ), and metal ions were used. The quantitative complexation of the ligands and FeII ions was monitored by electrochemical measurements in up to eight complexation cycles for linear oligomers of 3 and in up to four cycles for branched oligomers of 4 . STM observation of branched oligomers at low surface coverage showed an even distribution of nanodots of uniform size and shape, which suggests the quantitative formation of dendritic structures. The electron‐transport mechanism and kinetics for the redox reaction of the films of linear and branched oligomer wires were analyzed by potential‐step chronoamperometry (PSCA). The unique current‐versus‐time behavior observed under all conditions indicates that electron conduction occurs not by diffusional motion but by successive electron hopping between neighboring redox sites within a molecular wire. Redox conduction in a single molecular wire in a redox‐polymer film has not been reported previously. The analysis provided the rate constant for electron transfer between the electrode and the nearest redox‐complex moiety, k1 (s?1), as well as that for intrawire electron transfer between neighboring redox‐complex moieties, k2 (cm2 mol?1 s?1). The strong effect of the electrolyte concentration on both k1 and k2 indicates that the counterion motion limits the electron‐hopping rate at lower electrolyte concentrations. Analysis of the dependence of k1 and k2 on the potential gave intrinsic kinetic parameters without overpotential effects: k10=110 s?1, k20=2.6×1012 cm2 mol?1 s?1 for [n Fe 3 ], and k10=100 s?1, k20=4.1×1011 cm2 mol?1 s?1 for [n Fe 4 ] (n=number of complexation cycles). 相似文献
37.
Akira Watanabe 《Tetrahedron letters》2004,45(33):6229-6233
Oxovanadium(V)(salen) complex 4 was found to catalyze Meerwein-Ponndorf-Verley cyanation of aliphatic aldehydes with good to high enantioselectivity. This cyanation showed a positive nonlinear effect. 相似文献
38.
Microgel-like poly(allyl methacrylate) (PAMA nanosphere) was prepared by the emulsion polymerization of AMA as the reactive crosslinked polymer nanosphere with abundant pendant allyl groups. The terpolymerization of PAMA nanosphere with allyl benzoate (ABz) and vinyl benzoate (VBz) was conducted in bulk using benzoyl peroxide as initiator at 80 °C. The gelation depended on the feed ABz/VBz molar ratio since the molecular weights of resulting poly(ABz-co-VBz)s that act as the bridges increased with an increase in the mole fraction of VBz in the feed monomer. Beyond the gel point, the sol was rapidly incorporated into the gel and the increasing tendency of the gel fraction became steeper from 70 to 95 mol% of VBz as a reflection of increased chain length of bridge between PAMA nanospheres. Moreover, the swelling ratio became lower with increasing the mole percentage of VBz in the feed monomer. These results would support the preferential incorporation of PAMA nanosphere into the gel and the longer bridge can capture more nanospheres to give a much shrunken gel. 相似文献
39.
Matsumoto T Kamada Y Sugimoto T Tada T Noguchi S Nakazumi H Shiro M Yoshino H Murata K 《Inorganic chemistry》2003,42(17):5192-5201
Two donor molecules newly synthesized, dimethylthio- and ethylenedithio-tetrathiafulvalenothioquinone-1,3-diselenolemethides (1 and 2), were used to prepare their charge-transfer (CT) salts with a magnetic FeBr(4)(-) counteranion. For 1, a low electrical conducting 1:1 salt (1.FeBr(4)) was obtained, in which molecules of 1 are tightly dimerized in a one-dimensional (1D) stacking column. On the other hand, 2 gave a 2:1 salt (2(2).FeBr(4)) as two different kinds of plate crystals (I and II). Both I and II possess similar stacking structures of molecules of 2 in each 1D column with a half-cut pipelike structure along the c axis. However, for I, the stacking columns are aligned in the same direction along the a and b axes, while for II they are in the same direction along the a axis, but in the reverse direction along the b axis, resulting in the difference in the relative arrangement of molecules of 2 and FeBr(4)(-) ions between the two crystals. The room-temperature electrical conductivities of the single crystals of I and II were 13.6 and 12.7 S cm(-)(1), respectively. The electrical conducting behavior in I was metallic above 170 K but changed to be semiconducting with a very small activation energy of 7.0 meV in the temperature range 4-170 K. In contrast, II showed the semiconducting behavior in the whole temperature range 77-285 K. The corresponding nonmagnetic GaBr(4)(-) salts with almost the same crystal structure as I and II showed definitively different electrical conducting properties in the metal to semiconductor transition temperature in I as well as in the magnitude of activation energy in the semiconducting region of I and II. The interaction between the d spins of FeBr(4)(-) ions was weak and antiferromagnetic in both I and II, but the magnitude of the spin interaction was unexpectedly larger compared with that in the FeBr(4)(-) salt of the corresponding sulfur derivative of 2 with closer contact between the neighboring FeBr(4)(-) ions. These electrical conducting and magnetic results suggest a significant interaction between the conducting pi electrons and the d spins of FeBr(4)(-) ions located near the columns or layers. 相似文献
40.
K. Komura K. Komura Y. Kuwahara Y. Kuwahara T. Abe T. Abe K. Tanaka K. Tanaka Y. Murata Y. Murata M. Inoue M. Inoue 《Journal of Radioanalytical and Nuclear Chemistry》2006,269(2):511-516
Summary Extremely low activity levels of cosmic ray induced nuclides have been measured in freshly precipitated rainwater by quick
chemical separation coupled with ultra low background gamma-spectrometry. The nuclides detected were 38S (T1/2 = 2.83 h)-38Cl (37.2 m), 39Cl (55.6 m), 24Na (14.96 h), 28Mg (20.9 h), 7Be (53.3 d) and 22Na (2.602 y). The number of atoms in rain water were evaluated to be ranging from 400-1900 l-1 for 39Cl (n = 6, mean: 1200), 30-1500 l-1 for 24Na (n = 16, mean: 520), 80-600 l-1 for 28Mg (n = 13, mean: 260), 1 . 106-4 . 107 l-1 for 7Be (n = 16, mean: 7 . 106) and 2 . 103-1 . 105 l-1 for 22Na (n = 9, mean: 2 . 104). Measurements of activity levels and activity ratios of short-lived cosmic-ray induced short-lived nuclides will open new
method to understand atmospheric processes occurred at the altitude of rain cloud. 相似文献