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51.
Electron-phonon interactions in the photoinduced excited electronic states in molecular systems such as phenanthrene-edge-type hydrocarbons are discussed and compared with those in the monoanions and cations. The complete phase patterns difference between the highest occupied molecular orbitals (HOMO) and the lowest unoccupied molecular orbitals (LUMO) (the atomic orbitals between two neighboring carbon atoms combined in phase (out of phase) in the HOMO are combined out of phase (in phase) in the LUMO) are the main reason that the C-C stretching modes around 1500 cm(-1) afford much larger electron-phonon coupling constants in the excited electronic states than in the charged electronic states. The frequencies of the vibrational modes that play an essential role in the electron-phonon interactions for the excited electronic states are similar to those for the monoanions and cations in phenanthrene-edge-type hydrocarbons. Possible electron pairing and Bose-Einstein condensation in the photoinduced excited electronic states as well as those in the monoanions and cations in molecular systems such as phenanthrene-edge-type hydrocarbons are also discussed. 相似文献
52.
S Sakurai K Mitani S Hashimoto K Morikawa S Yasuda E Koshinaka H Kato Y Ito 《Chemical & pharmaceutical bulletin》1992,40(6):1443-1451
To find a novel alpha-blocker with high alpha-blocking selectivity against dopamine D2-receptor affinity, we performed structural modification of the alkylene chains and the substituents on two benzene rings of 2-alkoxy-5-[(phenoxyalkylamino)alkyl]benzenesulfonamide derivatives. The modification of the alkylene chain between the amino moiety in the center of the molecule and the benzene ring (ring A) was found to be the most significant. 5-[2-[[2-(5-Fluoro-2-methoxyphenoxy)ethyl]amino]propyl]-2- methoxybenzenesulfonamide (II-4), which possesses 1-methylethyl as the alkylene chain, exhibited high alpha-blocking selectivity as well as potent alpha-blocking activity. 相似文献
53.
Aryltetralone lignans bearing methylenedioxy groups (1a-b; 2a-b) were isolated from seeds of Virola sebifera. Their antioxidant activities were evaluated by inhibition of lipid peroxidation as indicated by TBARS and chemiluminescence emission (CL) assays. The lignan 1c, 'having a 2'-hydroxy-4',5'-methylenedioxyphenyl group, was the most active compound with TBARS/CL Q 1/2 values of 0.89 and 0.10 microg/mL, respectively. The catechol derivatives 3 and 4, obtained by demethylenation of lignans 1a and 2a, were of similar activity to 1c, and all were much more effective as antioxidants than alpha-tocopherol. 相似文献
54.
Masao Kato Yutaka Takemoto Yasuhiko Nakano Masahiro Yamazaki 《Journal of polymer science. Part A, Polymer chemistry》1975,13(8):1901-1910
Some unsaturated monomers bearing hindered phenol and arylamine groups capable of forming stable radicals were prepared. Radical polymerizations of vinyl monomers having such groups were investigated with the use of azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, and tetraethylthiuram disulfide as initiator. Polymerizations of these monomers went normally only when azobisisobutyronitrile was used as initiator. The other initiators inhibited polymerizations remarkably or completely. The results suggest that radicals resulting from benzoyl peroxide and cumene hydroperoxide or tetraethylthiuram disulfide abstract hydrogen of the phenol or the amine to produce the stable radicals, thereby inhibiting the polymerization. Meanwhile, carbon radicals resulting from azobisisobutyronitrile add selectively to the vinyl double bonds of the monomers to initiate the polymerizations. The vinyl derivatives as well as allyl derivatives and cinnamic acid derivatives copolymerize easily with conventional monomers such as styrene, maleic anhydride, and butadiene, again, only when azobisisobutyronitrile was used as initiator. Antioxidative properties for styrene copolymers and butadiene-styrene copolymers incorporating the hindered phenol monomers were investigated. 相似文献
55.
A simple and effective method of preparing fast-response gels is developed. The freeze-drying and subsequent rehydration of thermosensitive gels alters the microstructural properties of the gels in a way that leads to rapid shrinking rates. Microporous hydroxypropyl cellulose (HPC) gels were created by this method to investigate the influence of the process on the swelling and shrinking kinetics of the gels in response to temperature changes. Micropores of different size ranges were produced by freezing gels with different amounts of water at −20 °C. Water content was the key factor to control the microporosity and the shrinking rates of gels. After the freezing treatment, an effective diffusion coefficient for shrinking could be determined by fitting Fick's law to the data (5.2 × 10−4 cm2/s). This was an increase of two orders of magnitude over that of the untreated, non-porous gel (6.0 × 10−6 cm2/s). The magnitude of the shrinking coefficient indicates that the shrinking rate of the microporous gel is probably limited by the convective flow, as unsteady flow through porous media follows the same differential equation as Fick's law, but with much greater transport coefficients, as observed here. Physically, the shrinking rate may be determined by the level of interconnected-cells in a microporous structure present at the beginning of shrinking process because the convection through the interconnected-cells is estimated to be much slower than the polymer network diffusion rate of the struts of micropores (0.1–3.0 μm) as well as heat transfer. 相似文献
56.
Nogami Masayuki Nagakura Takehito Hayakawa Tomokatsu Kasuga Toshihiro 《Journal of Sol-Gel Science and Technology》2000,19(1-3):253-256
Persistent spectral hole burning was studied in Eu3+ ions-doped Al2O3-SiO2 glass prepared by a sol-gel method. The gel synthesized by the hydrolysis of Si- and Al-alkoxides and EuCl3·6H2O was heated in air and hydrogen gas atmospheres. For the glass heated in air to contain OH bonds, the hole was formed by the photoinduced rearrangement of the OH bonds surrounding the Eu3+ ions, and was thermally refilled and erased above 200 K. On the other hand, the glass heated in hydrogen gas showed the hole spectrum above 200 K. It was found that the hole depth was independent of the temperature and was 7% of the total intensity at room temperature. The proposed mechanism was the electron transfer between the Eu3+ ions and the defect centers formed in glass matrix. 相似文献
57.
[reaction: see text] Regioselectivity of the oxidative coupling of 5,10,15-triarylporphyrin metal complexes with DDQ-Sc(OTf)(3) was dependent on the central metal and meso-aryl substituent. Oxo-quinoidal porphyrin was obtained from Ni(II) porphyrin under the same conditions. 相似文献
58.
M. Nakagawa S. Kato H. Fukazawa Y. Hasegawa J. Miyazawa T. Hino 《Tetrahedron letters》1985,26(48):5871-5874
Oxytryptophans 3, which are readily obtained by dye-sensitized photooxygenation of tryptophan followed by acid treatment, undergo a facile N,N′-transacylation to give the 3-(2-aminophenyl)-2-pyrrolidones 4 in the absence of oxygen, whereas in the presence of oxygen 3a was oxidized to kynurenine. 相似文献
59.
60.
Masayuki Yamane 《Journal of Sol-Gel Science and Technology》1997,8(1-3):483-487
A thick silica gel film, corresponding to the glass film of 10–20 micron in thickness, has been formed at the interface between
two immiscible liquids, hexane and water, using E-40, a partially polymerized silicon alkoxide, as the precursor. The film
formation was possible using both acid- and base-catalyzed water, but was greatly dependent on the type of catalyst. Only
the trace of a film was observed for the system catalyzed with a strong electrolyte such as HCl, HNO3 or NaOH, while a gel film, corresponding to the glass film of several to 10 micron in thickness was formed with a weak electrolyte
such as ammonia, organic acid like acetic acid, citric acid, etc., of similar pH value. The direct introduction of organic
base catalyst like triethylamine in hexane was much more effective than the use of ammonia water, suggesting that the polymerization
of E-40 to form a gel film takes place in the organic phase, where water molecules, as well as undissociated ammonia or organic
acids, can diffuse in. 相似文献