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31.
Mahesh Datt Bhatt Akihisa Baba Takeaki Sakurai Katsuhiro Akimoto 《Journal of Solid State Electrochemistry》2012,16(3):1141-1149
We have performed ultraviolet photoelectron spectroscopy measurements and density functional theory calculations to study
the electronic structure at the interface between organic semiconductor (3-(4-biphenylyl)-4-phenyl-5-(4-tert-butyl phenyl)-1,2,4-triazole
(TAZ)) and metals (Ca, Mg, Ag, and Au). The basic mechanism of interface states at organic–metal interfaces can be understood
by controlling the injection of charge carriers at these interfaces. The position of highest occupied molecular orbital relative
to the Fermi level and the magnitude of the interface dipole are measured for each organic–metal interface. For TAZ on Ca,
Mg, and Ag, interface states are observed near the Fermi level. However, no interface state is observed for TAZ on Au. It
is analyzed qualitatively that the interface state is formed due to interaction of TAZ lowest unoccupied molecular orbital
composed of C2p and metal s levels. It is suggested that the interface state plays an important role in charge transport at
the interface. The mechanism of formation of interface states and electrical properties are discussed. 相似文献
32.
Murashima K Watanabe T Kanegawa S Yoshihara D Inagaki Y Karasawa S Koga N 《Inorganic chemistry》2012,51(9):4982-4993
N,N-Dipyridilaminoxyl, NOpy(2), having a stable aminoxyl, was prepared as a new magnetic coupler for heterospin systems. Solutions of NOpy(2) were mixed with those of bis{1,1,1,5,5,5, hexafluoro-4-(phenylimino)-2-pentanonate}cobalt derivatives, Co(hfpip-X)(2), at a 1:1 ratio to afford the polymeric cobalt(II) complexes, [Co(hfpip-X)(2)(NOpy(2))](n); X = H (1), F (2), F(3) (3), F(5) (4), Cl (5), Cl(3) (6), Br (7), and I (8) as single crystals. In all complexes, the local structures of the cobalt-complex units were compressed octahedra and the pyridine ligands in NOpy(2) units coordinated to the cobalt ions in trans configuration to form linear chains for 1-4 and in cis configuration to form helical chains for 5-8. In the chains, the aminoxyl in NOpy(2) ferromagnetically interacted with the cobalt ions to produce the ferromagnetic chains with J(intra)/k(B) = 9-14 K. In the magnetic susceptibility experiments of aligned sample of 6, the magnetic easy axis was determined to be the a* axis, which was the direction perpendicular to the b axis of the chain axis. The resulting chains, all except 4, interacted antiferromagnetically among each other, and especially in 1, 5, 7, and 8, the magnetic behaviors characteristic to canted two-dimensional (2D) antiferromagnets with T(c) = 5.6, 4.0, 4.0, and 6.2 K, respectively, were observed. All complexes showed slow magnetic relaxations affected by the interchain antiferromagnetic interaction. The effective activation barriers, Δ(eff)/k(B), for the reorientation of the magnetism for all complexes except 4 were estimated to be 25-39 K in the presence of a direct current (dc) field. 相似文献
33.
We investigate volume phase transition in gels immersed in mixture solvents, on the basis of a three-component Flory-Rehner theory. When the selectivity of the minority solvent component to the polymer network is strong, the gel tends to shrink with an increasing concentration of the additive, regardless of whether it is good or poor. This behavior originates from the difference of the additive concentration between inside and outside the gel. We also found the gap of the gel volume at the transition point can be controlled by adding the strongly selective solutes. By dissolving a strongly poor additive, for instance, the discontinuous volume phase transition can be extinguished. Furthermore, we observed that another volume phase transition occurs far from the original transition point. These behaviors can be well explained by a simplified theory neglecting the nonlinearity of the additive concentration. 相似文献
34.
A new imaging system based on optical frequency domain reflectometry is presented. The intensity-integration effect of the
charge coupled device camera to be used acts effectively as a low pass filter for the intensity fluctuation and the 2nd order
moment of the detected signals is proportional to a low beat frequency component of the interference signal. Consequently,
two-dimensionally imaging of the reflectance of a selective plane located in scattering media is demonstrated. 相似文献
35.
Takeaki Kariya Yoshihiko Konno William E. Strawderman 《Journal of multivariate analysis》1996,56(2):245-258
In the GMANOVA model or equivalent growth curve model, shrinkage effects on the MLE (maximum likelihood estimator) are considered under an invariant risk matrix. We first study the fundamental structure of the problem through which we decompose the estimation problem into some conditional problems and then demonstrate some classes of double shrinkage minimax estimators which uniformly dominate the MLE in the matrix risk. 相似文献
36.
Shin-Ichi Takahashi Tetsuya Fujimoto Basu M. Barua Takeaki Miyamoto Hiroshi Inagaki 《Journal of polymer science. Part A, Polymer chemistry》1986,24(11):2981-2993
13C-NMR spectra of trityl cellulose (Tr-Cell), tosyl cellulose (Ts-Cell), cellulose S-methyl xanthate (Cell-M-Xan), and cellulose formate (CF) in dimethylsulfoxide-d6 were analyzed at 50.4 MHz. It was found that the distribution of substituents in the anhydroglucose units of these cellulose derivatives can be estimated from their ring carbon spectra. The results showed that (i) in Tr-Cell having degree of substitution (DS) lower than 1, the hydroxyl groups at C-6 carbon position are selectively tritylated, (ii) in the case of Ts-Cell, the difference in the relative DS value among three different types of hydroxyl groups is not large, although the relative reactivities of hydroxyl groups toward tosylation decrease in the order C-6 > C-2 > C-3, (iii) in Cell-M-Xan, the hydroxyl groups at C-3 carbon position are mainly substituted, and (iv) the ease of formylation is C-6 > C-2 > C-3. The 100.8 MHz 13C-NMR spectra of O-methyl cellulose (MC) revealed that the reactivity order in commercial MC prepared from alkali cellulose is C-6 ? C-2 > C-3. Concerning MC, its water solubility was also discussed in terms of the distribution of substituents along the cellulose chain. 相似文献
37.
The bicyclic core, furo[3,2-b]pyran, of the dysiherbaines has been synthesized via two routes involving the imino 1,2-Wittig rearrangement of allyl furohydroximate and the asymmetric dihydroxylation of furylpropenol derivative. 相似文献
38.
A new function that effectively takes into account ring structural environments achieves extensive highly accurate prediction of 13C NMR chemical shift in the CAST/CNMR system. The approach adapts a fast and flexible ring perception algorithm and a new CAST coding method for the ring information. 13C NMR chemical shift prediction is performed for complicated polycyclic natural products and their synthetic intermediates as the demonstration, which shows the reliability of the function in extending the scope of the practically accurate 13C NMR prediction for wide range of organic compounds. 相似文献
39.
Ueda M Miyabe H Teramachi M Miyata O Naito T 《The Journal of organic chemistry》2005,70(17):6653-6660
The intermolecular radical addition to chiral nitrones 2, 4, 5, and 16 was studied. The isopropyl radical addition to Oppolzer's camphorsultam derivative 2 of glyoxylic nitrone proceeded with excellent diastereoselectivity to give the desired isopropylated product 3a accompanied by the diisopropylated product 3b. A high degree of stereocontrol in the reaction of cyclic nitrone 4 was achieved. The ethyl radical addition to nitrone 4 with triethylborane afforded the desired ethylated product 9a accompanied by the diethylated product 10a and the ethylated nitrone 11a. To evaluate the utility of cyclic nitrone 4, several alkyl radicals were employed in the addition reaction, which afforded the alkylated products 9b-d with excellent diastereoselectivities. In the presence of Mg(ClO(4))(2), the ethyl radical addition to BIGN 16 afforded selectively syn isomers. In contrast, the alkyl radical addition to 16 took place even in the absence of Lewis acid to give anti isomers. 相似文献
40.
We have developed a cationic rhodium(I)/BINAP complex-catalyzed isomerization of secondary propargylic alcohols to alpha,beta-enones. The asymmetric variant of this reaction, a kinetic resolution of secondary propargylic alcohols, was also developed with good selectivity. The mechanistic study revealed that the isomerization proceeds through intramolecular 1,3- and 1,2-hydrogen migration pathways. [reaction: see text] 相似文献