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111.
Noritaka Ohtani Yukihiko Inoue Hiroshi Mizuoka Kenya Itoh 《Journal of polymer science. Part A, Polymer chemistry》1994,32(13):2589-2595
Dilute-solution viscosities of polystyrene-based cationic ionomers containing ammonio or phosphonio groups were measured in several solvents. In polar solvents with dielectric constant (εr) beyond 10, the ionomers showed a typical polyelectrolyte behavior, indicating that a large part of ionic groups were dissociated into ions. In nonpolar solvents with low εr, the reduced viscosity of the ionomers linearly decreased with a decreasing ionomer concentration. At low polymer concentrations, every ionomer gave a reduced viscosity lower than that of the corresponding chloromethylated polystyrene. With an increasing ion content, the intrinsic viscosity progressively decreased if the nonpolar solvents had a low acceptor number (AN), such as toluene or tetrahydrofran (THF). In the halogenated solvents with high AN value, such as chloroform, however, the intrinsic viscosity was hardly dependent on the ion content. This indicates that the intramolecular aggregation among the ionic groups is inhibited in the halogenated solvents due to a strong anion solvation. An addition of a protic solvent to a nonpolar solvent eliminates the aggregation between ionic groups and leads to polyelectrolyte behavior. © 1994 John Wiley & Sons, Inc. 相似文献
112.
Masayuki Inoue 《Tetrahedron letters》2004,45(10):2053-2056
We report a new reaction for the direct construction of O,S-acetals, key intermediates in the assembly of fused polycyclic ethers. α-Fluorosulfides and secondary alcohols were coupled by the action of Yb(OTf)3 to generate O,S-acetals in high yield. The neutral and selective nature of the reaction should be useful for synthesizing natural and artificial polyethers with multisensitive functionalities. 相似文献
113.
A novel protocol for assembling polycyclic ethers was developed and successfully applied to the synthesis of the EFGH ring system of ciguatoxin CTX3C. A key transformation involves construction of an O,S-acetal through coupling of alpha-chlorosulfide and a secondary alcohol under mild conditions. The method is highly applicable to use with sensitive substrates and will enable the synthesis of various natural and artificial polycyclic ethers. [reaction: see text] 相似文献
114.
Tsutomu Shiragami Katsunori Tanaka Yoshito Andou Shin-ichiro Tsunami Jin Matsumoto Hongxia Luo Yasuyuki Araki Osamu Ito Haruo Inoue Masahide Yasuda 《Journal of photochemistry and photobiology. A, Chemistry》2005,170(3):287-297
Tetraphenylporphyrinatoantimony(V) complexes, linked to boron-dipyrrin chromophores on axial ligands, were synthesized. The fluorescence spectra of 1a, 1b and 1c (3-[4-(N,N′-difluorobornyl-5-dipyrrinyl)phenyl]propoxo(methoxo)antimony(V) tetraphenylporphyrin bromide (1a); 6-[4-(N,N′-difluorobornyl-5-dipyrrinyl)phenyl]hexyloxo(methoxo)antimony(V) tetraphenylporphyrin bromide (1b); bis{3-[4-(N,N′-difluorobornyl-5-dipyrrinyl)phenyl]propoxo}antimony(V) tetraphenylporphyrin bromide (1c)) were analyzed under the excitations of N,N′-difluorobornyl-5-dipyrrinylphenyl (Bdpy) and tetraphenylporphyrinatoantimony(V) (Sb(TPP)) chromophores. Under the irradiation of Bdpy chromophore, the excitation energy was transferred from Bdpy chromophore to the Sb(TPP) moiety at 0.13–0.40 of the quantum yields, even in a polar solvent. On the other hand, the emission of Sb(TPP) chromophores was quenched by Bdpy chromophores at rate constants of 108–109 s−1, independent of on the solvent polarity. Under the excitation of the Bdpy chromophore of 1d (3-[4-(N,N′-difluorobornyl-5-dipyrrinyl)phenyl]propoxo(phenyloxo)antimony(V) tetraphenylporphyrin bromide) involving both the Bdpy and the phenoxy chromophores on the axial ligands, the excited singlet state of the Sb(TPP) chromophore generated by the energy transfer from the Bdpy chromophore was quenched by the phenoxy ligand via non-radiative processes involving electron transfer. However, rapid back electron-transfer may occur because no absorption of the anion radical of Sb(TPP) was observed by nanosecond laser photolysis. 相似文献
115.
A simple method for the rapid and simultaneous analysis of dichlorvos (DDVP), malathion, carbaryl, and 2,4-dichlorophenoxy acetic acid (2,4-D) in citrus fruit, which uses flow-injection ion spray ionization tandem mass spectrometry, has been developed for the first time. The method involves the combined use of stable isotopically labeled internal standards (DDVP-d6, malathion-d10, carbaryl-d7, and 2,4-D-d5) and a multiple reaction monitoring technique. The average recoveries for the pesticides at the same concentrations as their tolerance levels (DDVP: 0.1-0.2 μg g−1; malathion: 0.5-4.0 μg g−1; carbaryl: 1.0 μg g−1; 2,4-D: 1.0-2.0 μg g−1) ranged from 90 to 119% with the relative standard deviation (R.S.D.) ranging from 1.0 to 13.1% (n = 5). Analysis time, including sample preparation and determination, was only 15 min. The present method is effective for screening DDVP, malathion, carbaryl, and 2,4-D in citrus fruit. 相似文献
116.
Summary HPLC determination of pheophytinatonicke(II) (Pheo-Ni) prepared by the replacement of magnesium(II) in chlorophyll with nicke(II)
is described. The good separation of PheoNi was obtained by using chemically bonded C18 as the stationary phase and acetone-methanol (50∶50, vol/vol) as the mobile phase. Conventional spectrophotometric method
was also used for the determination of PheoNi. For the synthetic samples prepared by mixing (pheophytinato a) nicke(II) [(Pheo-a)
Ni] and (pheophytinato b) nicke(II) [(Pheo-b) Ni], analytical values obtained by the spectrophotometric method were very high
compared to those obtained by HPLC. In the proposed HPLC method, (Pheo-a) Ni and (Pheo-b). Ni could be determined in the concentration
range of 0.028–30μg/ml and 0.038–30μg/ml with relative standard deviations (n=10) of 3.1% and 0.8%, respectively. 相似文献
117.
Spirobenzopyran 1 , with the 3-(diethoxymethylsilyl)-propyl group at the N atom, was synthesized. The condensation reaction of the spiropyran 1 and diethoxydimethylsilane gave oligomeric poly(dimethylsiloxane) with the spiropyran moiety in the side chain. The oligomer was photochromic; its colour changed from colorless to purple-red on uv irradiation and the color faded on visible irradiation or on standing in the dark. The half-decay time of the thermal decoloration was about twice that of monomeric spiropyran dissolved in the dimethylsiloxane oligomer. Photochromic poly(dimethylsiloxane) with the spirooxazine moiety in the side chain was also prepared. 相似文献
118.
Tongbu Lu Xin Wang Minyu Tan Yu Liu Yoshihisa Inoue Tadao Hakushi 《Helvetica chimica acta》1993,76(1):241-247
The lanthanide nitrate complexes with 13-crown-4(13-C-4) have been prepared in AcOEt. These new complexes with the general formula Ln(NO3)3.(13-c-4) (Ln = La–Nd, Sm–Lu) have been characterized by means of elemental analysis, IR and 1H-NMR spectra, conductivity measurements, and TG-DTA techniques. The crystal and molecular structure of Nd(No3)3. (13-c-4) has been determined by single crystal X-ray diffraction. It crystallizes in the monoclinic space group P21/a with Z = 8. Lattice parameters are a = 15.393(1), b = 12.578(1), c = 19.279(2) Å, β = 113.05(1)°, V = 3435 Å3, Dc = 2.01 g cm?3, μ = 31.0 cm?1 (Mok2), F(000) = 2056. The structure was solved by Patterson and Fourier techniques and refined by least-squares to a final conventional R value of 0.032 for 5218 independent reflections with I ? 3σ(I). There are two independent Nd(No3)3 · (13-C-4) monomers in one asymmetrical unit. The coordination numbers are ten in these two independent monomers. 相似文献
119.
120.