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21.
Hiroshi Mitsui Yuichi Shimizu 《Journal of polymer science. Part A, Polymer chemistry》1980,18(3):1115-1122
The γ radiolysis of polyethylene preirradiated with electron beams to 3 Mrad was carried out at 30–100°C in vacuo with a dose rate of 6.35 × 105 rad/hr. The hydrogen formation in the γ radiolysis was little affected by the preirradiation of electron beams, whereas the formation of trans-vinylene unsaturation and gel was somewhat retarded. The rates of the formation of hydrogen and trans-vinylene unsaturation were described by the zero-order formation kinetics with respect to each concentration combined with the first-order disappearance. The apparent rate constants and activation energies for the formation and disappearance of hydrogen and trans-vinylene unsaturation were almost independent of the preirradiation. The gel fraction was analyzed by using the Charlesby–Pinner equation. The G values of crosslinking and main chain scission were increased by the preirradiation, whereas their activation energies remained unaltered. On the basis of these results the effects of preirradiation on the reactions induced by γ rays in polyethylene were discussed. 相似文献
22.
Optimal control simulation is applied to the cis-trans photoisomerization of retinal in rhodopsin within a two-dimensional, two-electronic-state model with a conical intersection [S. Hahn and G. Stock, J. Phys. Chem. B 104, 1146 (2000)]. For this case study, we investigate coherent control mechanisms, in which laser pulses work cooperatively with a conical intersection that acts as a "wave-packet cannon." Optimally designed pulses largely consist of shaping subpulses that prepare a wave packet, which is localized along a reaction coordinate and has little energy in the coupling mode, through multiple electronic transitions. This shaping process is shown to be essential for achieving a high target yield although the envelopes of the calculated pulses depend on the local topography of the potential-energy surfaces around the conical intersection and the choice of target. The control mechanisms are analyzed by considering the motion of reduced wave packets in a nuclear configuration space as well as by snapshots of probability current-density maps. 相似文献
23.
We have determined the crystal structure of the title compound, which has a triclinic cell with cell parameters of , , , α=76.617°, β=84.188°, γ=74.510° and space group . The crystal structure suggests the chemical formula CoMoO4·3/4H2O. The structure consists of MoO4 tetrahedra and CoO6 octahedra, confirming the earlier X-ray absorption near-edge spectroscopic (XANES) investigation on the hydrate. The comparison of the crystal structures of the hydrate and the α-,β-, and hp-phases shows that the hydrate exhibits metal cation coordinations similar to those of the β-phase, but had arrangements of CoO6 and MoOn polyhedra similar to those of the hp-phase. 相似文献
24.
Chiral urea compounds 10a-g were synthesized as catalysts for conjugate addition of pyrrolidine (2) to gamma-crotonolactone (3). In the presence of a catalytic amount of the chiral ureas, this hetero-Michael reaction was greatly accelerated. Asymmetric induction was observed with the catalysts 10e, 10f, and 10g. 相似文献
25.
M Kitagawa K Yamamoto S Katakura H Kanno K Yamada T Nagahara M Tanaka 《Chemical & pharmaceutical bulletin》1991,39(10):2681-2690
Di- and tri-substituted [(4-oxo-4H-1-benzopyran-7-yl)oxy]acetic acids, and 4-oxo-3-phenyl-4H-furo[2,3-h]-[1]benzopyran-8-carboxylic acid were synthesized and tested for natriuretic and uricosuric activities. Among the compounds tested, 3,5-disubstituted [(4-oxo-4H-1-benzopyran-7-yl)oxy]acetic acids (6c-f, h, n and x) showed potent natriuretic and uricosuric activities, whereas 4-oxo-3-phenyl-4H-furo[2,3-h][1]benzopyran-8-carboxylic acid (6dd) possessed only potent natriuretic activity. The structure-activity relationships are also discussed. 相似文献
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Onodera K Nakamura H Oba Y Ohizumi Y Ojika M 《Journal of the American Chemical Society》2005,127(29):10406-10411
Zooxanthellamide Cs (ZAD-Cs), C(128)H(220)N(2)O(53)S(2) (ca. 2.7 kDa), was obtained from a cultured marine dinoflagellate of the genus Symbiodinium as an inseparable isomeric mixture of polyhydroxylated 61- to 66-membered macrolides. The chemical structures of the components were clarified by detailed 2D NMR analysis to be the macrolactonized analogues of zooxanthellamide A (ZAD-A), which had been previously isolated from the same microalgae. Chemical lability of ZAD-Cs suggests that ZAD-A is an artifact derived from ZAD-Cs during the isolation steps. Three of the components possess the largest (63-, 64-, and 66-membered) ring sizes found to date among the natural macrolides. ZAD-Cs exhibited higher vasoconstrictive activity than that of the zooxanthellatoxins, the first vasoconstrictive macrolides from Symbiodinium sp. The structure-activity relationship suggests that the huge macrolactone structure is important for biological activity. The relationship between the structures of the polyol metabolites and the phylogenetic systematics of Symbiodinium sp. is also discussed. 相似文献
29.
Regioselective 1,4-addition of nucleophiles to 1,3-diene monoepoxides catalyzed by palladium complex
1,3-Diene monoepoxides react with nucleophiles in the presence of palladium complex as a catalyst under neutral conditions to give 1,4-adducts selectively. The 1,4-adducts are allylic alcohols and there is a possibility of another nucleophilic attack. Ester of Monarch butterfly pheromone was prepared. 相似文献
30.
Motoyama T Shimazaki Y Yajima T Nakabayashi Y Naruta Y Yamauchi O 《Journal of the American Chemical Society》2004,126(23):7378-7385
The Pd(II) complexes of new 2N1O-donor ligands containing a pendent indole, 3-[N-2-pyridylmethyl-N-2-hydroxy-3,5-di(tert-butyl)benzylamino]ethylindole (Htbu-iepp), 1-methyl-3-[N-2-pyridylmethyl-N-2-hydroxy-3,5-di(tert-butyl)benzylamino]ethylindole (Htbu-miepp), 3-[N-2-pyridylmethyl-N-2-hydroxy-3,5-di(tert-butyl)benzylamino]methylindole (Htbu-impp), and 3-(N-2-pyridylmethyl-N-4-hydroxybenzylamino)ethylindole (Hp-iepp) (H denotes a dissociable proton), were synthesized, and the structures of [Pd(tbu-iepp)Cl] (1a), [Pd(tbu-iepp-c)Cl] (1b), [Pd(tbu-miepp)Cl] (3), and [Pd(p-iepp-c)Cl] (4) (tbu-iepp-c and p-iepp-c denote tbu-iepp and p-iepp bound to Pd(II) through a carbon atom, respectively) were determined by X-ray analysis. Complexes 1a prepared in CH(2)Cl(2)/CH(3)CN and 3 prepared in CH(3)CN have a pyridine nitrogen, an amine nitrogen, a phenolate oxygen, and a chloride ion in the coordination plane. Complex 1b prepared in CH(3)CN has the same composition as 1a and was revealed to have the C2 atom of the indole ring bound to Pd(II) with the Pd(II)-C2 distance of 1.973(2) A. The same Pd(II)-indole C2 bonding was revealed for 4. Interconversion between 1a and 1b was observed for their solutions, the equilibrium being dependent on the solvent used. Reaction of 1b and 4 with 1 equiv of Ce(IV) in DMF gave the corresponding one-electron-oxidized species, which exhibited an ESR signal at g = 2.004 and an absorption peak at approximately 550 nm, indicating the formation of the Pd(II)-indole pi-cation radical species. The half-life, t(1/2), of the indole radical species at room temperature was calculated to be 20 s (k(obs) = 3.5 x 10(-)(2) s(-)(1)) for 1b. The cyclic voltammogram for 1b in DMF gave two irreversible oxidation peaks at E(pa) = 0.68 and 0.80 V (vs Ag/AgCl), which were ascribed to the oxidation processes of the coordinated indole and phenolate moieties, respectively. 相似文献