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891.
Susumu Fujimori Haruhiko Nakajima Yasaku Wada Masao Doi 《Journal of Polymer Science.Polymer Physics》1975,13(11):2135-2153
A Langevin equation of motion for a charged bead-spring statistical chain is written in difference form and the relaxation and equilibrium behavior of the chain is studied by computer simulation. Results are presented for the behavior of end-to-end length h, principal axes of the polymer ellipsoid L1, L2, L3, and chain contour length c in terms of their averages, root mean square values, root mean square fluctuations, orientations, and relaxation strengths and times. The simulation was made with various sets of parameters, bead number N, charge on the bead q, and radius of ion atmosphere around the bead k?1. It is found that 〈h2〉1/2 and 〈L12〉1/2 increase more strongly with increasing q and decreasing κ than 〈L22〉1/2, 〈L32〉1/2, and 〈c12〉1/2, indicating that the chain is expanded in three dimensions and at the same time is extended along the end-to-end direction. The relaxation time τrot of rotation of the end-to-end vector, which is proportional to N2 at q = 0, increases with increasing q and tends to be proportional to N3 for an extended chain, while the relaxation time τconf of the magnitude of h is almost independent of q and is always proportional to N2. It is concluded that the extended chain possesses a well-defined end-to-end axis and the chain rotates as a whole with a relaxation time τrot which is much longer than τconf. The complex viscosity of the chain is calculated from the Fourier transform of the time–correlation function of momentum flux and is found to have a frequency spectrum similar to that observed for aqueous solutions of poly(acrylic acid). The dominant mode appearing in the low-frequency range is evidenced to arise from the rotation of the extended chain. 相似文献
892.
893.
894.
Titanium tetrachloride is a very effective catalyst for the addition of lithium aluminum hydride to olefins. This facile reaction provides a convenient laboratory method for the selective reduction of nonconjugated diolefins or for the selective preparation of haloolefins from diolefins. 相似文献
895.
896.
Toshiko Tanimoto Yuko Kishimoto Akiko Ikuta Yuki Nishi Keishiro Miyake 《Journal of inclusion phenomena and macrocyclic chemistry》2002,44(1-4):297-302
Branched -cyclodextrins (-CDs) having manno-oligosaccharide side chains were investigated. Three kinds of monobranched -CDs and five kinds of dibranched -CDs were chemically synthesized using the trichloroacetimidate method. Their structures were analyzed by HPLC, MS, and NMR spectroscopies. The specific interaction between those compounds and mannose-binding lectins (Concanavalin A and Pisum sativum agglutinin) was investigated by inhibition tests of hemagglutinating activity and by using an optical biosensor of the IAsys apparatus with a resonant mirror detector. The results showed that all branched -CDs interactedwith lectins. The binding affinity was 61,64-(Man3)2- 61,64-(Man2)2- > 61,64-(Man4)2--CD when the derivatives were compared on the basis of side chain length and 61,63- 61,64- > 61,62-(Man2)2--CD when compared on the basis of side chain position. 相似文献
897.
Yaoita Y Kohata R Kakuda R Machida K Kikuchi M 《Chemical & pharmaceutical bulletin》2002,50(5):681-684
Five mushrooms, Panellus serotinus, Lyophyllum connatum, Amanita pantherina, Sarcodon aspratus and Lepista nuda, have been investigated chemically. Two new ceramides, (2S,3R,4E,8E)-N-hexadecanoyl-2-amino-9-methyl-4,8-octadecadiene-1,3-diol (1) and (2S,3R,4E,8E,9'Z,12'Z)-N-9',12'-octadecadienoyl-2-amino-9-methyl-4,8-octadecadiene-1,3-diol (2), have been isolated from Panellus serotinus. Compound 2 was also isolated from Lyophyllum connatum. Two new ceramides, (2S,2'R,3R,4E,8E)-N-2'-hydroxypentadecanoyl-2-amino-9-methyl-4,8-octadecadiene-1,3-diol (4) and (2S,2'R,3R,4E,8E)-N-2'-hydroxytetradecanoyl-2-amino-9-methyl-4,8-octadeca-diene-1,3-diol (5), have been isolated from Amanita pantherina with (2S,2'R,3R,4E,8E)-N-2'-hydroxyhexadecanoyl-2-amino-9-methyl-4,8-octadecadiene-1,3-diol (3), a known synthetic compound. Compounds 3 and 4 were also isolated from Sarcodon aspratus and compound 3 was isolated from Lepista nuda. The structures of the new compounds were elucidated on the basis of their spectral data. 相似文献
898.
Toyota M Shimamura T Ishii H Renner M Braggins J Asakawa Y 《Chemical & pharmaceutical bulletin》2002,50(10):1390-1392
The ether extract of the New Zealand liverwort Radula marginata afforded a new cannabinoid type bibenzyl compound named perrottetinenic acid, and two new bibenzyls, together with a known cannabinoid, perrottetinene. Their structures were established by two dimensional (2D) NMR spectral data. The structure of perrottetinenic acid was a similar to that of Delta(1)-tetrahydrocannabinol, a known hallucinogen. Cannabinoid type bibenzyls have been isolated from liverwort Radula perrottetii, though have not previously been reported from the liverwort R. marginata. 相似文献
899.
Yamada K Unno M Kobayashi K Oku H Yamamura H Araki S Matsumoto H Katakai R Kawai M 《Journal of the American Chemical Society》2002,124(43):12684-12688
An X-ray crystallographic analysis of the bis-Ndelta-Boc-tetra-Nalpha-methyl derivative of gramicidin S, cyclo(-Val-MeOrn(Boc)-Leu-d-MePhe-Pro-)2, was undertaken successfully (R-factor = 0.088). As expected, the main chain adopts an antiparallel pleated beta-sheet conformation, but the pleated sheet is slightly twisted, and the sense of twisting is opposite to that found in the reported crystal structures of the gramicidin S-urea complex and the bis-Ndelta-(trichloroacetyl) and bis-Ndelta-(m-bromobenzoyl) derivatives of gramicidin S. In agreement with the observed resistance toward N-methylation, the urethane NH groups of the protected Orn side chains are hydrogen bonded to the carbonyl groups of the d-Phe residues. However, the side-chain-main-chain hydrogen bonding is in the i --> i - 3 mode, although hydrogen bonding in the i --> i + 2 mode was deduced from a 1H NMR study of protected gramicidin S derivatives and was actually found in the crystal structures of the diacylated gramicidin S. 相似文献
900.
K. Gibasiewicz R. Naskrecki M. Ziółek M. Lorenc J. Karolczak J. Kubicki J. Goc J. Miyake A. Dobek 《Journal of fluorescence》2001,11(1):33-40
Electron transfer in the reaction center of the purple photosynthetic bacterium Rb. sphaeroides R-26 has been studied at room temperature by transient absorption spectroscopy with a time resolution of 120 fs. Measurements of absorption changes were performed in the range from 400 nm up to 680 nm, after excitation with a laser pulse of 80 fs duration within the absorption band of the bacteriochlorophyll at 800 nm. The excited state of the primary donor, characterized by the absorbance changes extending over the whole spectral range investigated, appeared within 120 fs and gave rise to the bleaching of the Qx absorption band of bacteriochlorophyll at 600 nm, increased further by electron transfer to bacteriopheophytin in 3 ps. Photoreduction of the bacteriopheophytin acceptor detected at 546 nm and 670 nm proceeded with the same time constant. Multiphase absorbance changes were relatively the largest in the blue spectral range between 415 nm and 450 nm. Apart from the immediate absorbance increase due to excitation of the primary donor, another fast increasing phase was detected characterized by a wavelength dependent time constant—from 5.5 ps at 415 nm to 1.9 ps at 450 nm. Both the photooxidised primary donor and photoreduced bacteriopheophytin contributed to the amplitude of this phase. The electron transfer from the reduced bacteriopheophytin to a quinone acceptor was observed as a decrease in the intensity of the transient absorption bands at about 422 nm and at 670 nm, with disappearance of the bleaching at 546 nm and increase of the bleaching at 600 nm, all in 200 ps. 相似文献