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921.
Fujii K Fujimori T Takamuku T Kanzaki R Umebayashi Y Ishiguro S 《The journal of physical chemistry. B》2006,110(16):8179-8183
The structure of bis(trifluoromethanesulfonyl) imide (TFSI-) in the liquid state has been studied by means of Raman spectroscopy and DFT calculations. Raman spectra of 1-ethyl-3-methylimidazolium (EMI+) TFSI- show relatively strong bands arising from TFSI- at about 398 and 407 cm(-1). Interestingly, the 407 cm(-1) band, relative to the 398 cm(-1) one, is appreciably intensified with raising temperature, suggesting that an equilibrium is established between TFSI- conformers in the liquid state. According to DFT calculations followed by normal frequency analyses, two conformers of C2 and C1 symmetry, respectively, constitute global and local minima, with an energy difference 2.2-3.3 kJ mol(-1). The wagging omega-SO2 vibration appears at 396 and 430 cm(-1) for the C1 conformer and at 387 and 402 cm(-1) for the C2 one. Observed Raman spectra over the range 380-440 cm(-1) were deconvoluted to extract intrinsic bands of TFSI- conformers, and the enthalpy of conformational change from C2 to C1 was evaluated. The enthalpy value is in good agreement with that obtained by theoretical calculations. We thus conclude that a conformational equilibrium is established between the C1 and C2 conformers of TFSI- in the liquid EMI+TFSI-, and the C2 conformer is more favorable than the C1 one. 相似文献
922.
The dielectric relaxation behavior of aqueous triethylammonioalkanoate (carbobetaine: Et(3)nCB) solutions was examined as a function of frequency from 1.00 x 10(6) to 2.00 x 10(10) Hz (6.28 x 10(6) to 1.26 x 10(11) rad s(-1) in angular frequency); number of intercharge methylene groups, n = 1, 3, 4, 5, and 10; and solute concentration, c. Two major relaxation modes, fast and slow, were found in all solutions examined. Et(3)nCB systems with n = 5 and 10 possessed another, medium, relaxation mode with relaxation time tau(Dh) at high c values (above the contact concentration of solutes) in addition to the fast and slow modes. The fast mode with a relaxation time, tau(w), of approximately 10 ps was attributed to the rotational motion of bulk water molecules. The slow mode with a relaxation time, tau, of 0.08-1 ns, depending on the n value, was attributed to the overall rotational motion of each carbobetaine in aqueous solution. The concentration normalized relaxation strength, Deltaepsilonc(-1), and tau value of the slow relaxation mode increased with increasing n. These findings were quantitatively explained on the basis of changes in the intercharge distance resulting in increased size and dipole moment of the carbobetaines. Above the contact concentration, collisions between solute molecules likely hindered their rotational motions, leading to an increase in tau. The middle relaxation mode found in longer Et(3)nCBs (n = 5 and 10) with a relaxation time, tau(Dh), of approximately 0.2 ns, more than 20 times as long as that of bulk water molecules, tau(w), was attributed to the dehydration of water molecules tightly bound to all Et(3)nCBs examined (including those with n < 5). This mode was not observed in the solutions of Et(3)nCBs with n < 5, since the tau values corresponding to overall rotation were close to or shorter than the tau(Dh) values. 相似文献
923.
The hydration state of poly(ethylene oxide)s (PEOs) in aqueous solutions was investigated using dielectric relaxation measurements at 25 degrees C over a frequency range up to 20 GHz, which is the relaxation frequency of water molecules in a bulk state. The dielectric relaxation spectra obtained indicated decomposition into two major and one minor relaxation modes with relaxation times of 8.3, 22, and 250 ps, respectively. The two major modes were attributed to rotational relaxation of water molecules belonging to the bulk state and water molecules hydrogen bonded to ethylene oxide (EO) monomer units. The number of hydration water molecules per EO unit depended on the molar mass of PEO (M) and reached a constant value of 3.7 at M > 1500, which agrees with the value obtained by other experiments. 相似文献
924.
We give congruences between the Eisenstein series and a cusp form in the cases of Siegel modular forms and Hermitian modular forms. We should emphasize that there is a relation between the existence of a prime dividing the (k?1)th generalized Bernoulli number and the existence of non-trivial Hermitian cusp forms of weight k. We will conclude by giving numerical examples for each case. 相似文献
925.
Toshiyuki Itoh Manabu Kanbara Shino Nakajima Yusuke Sakuta Shuichi Hayase Motoi Kawatsura Takashi Kato Kazutoshi Miyazawa Hidemitsu Uno 《Journal of fluorine chemistry》2009,130(12):1157-1163
The synthesis of a novel spiro type gem-difluorocyclopropane building block, 1,1,7,7-tetrafluoro-2,8-bis(hydroxymethyl)dispiro[2.2.2.2]decane (1), has been accomplished in optically pure form using chemo-enzymatic reaction protocol. Various types of diesters or dialkyl ether were prepared from diol (+)-1 or (−)-1 in optically active form and their helical twisting power (HTP) was evaluated by addition of 1.0 wt% to a non-chiral nematic liquid crystal host. Although their HTP values were not significant, all compounds showed liquid crystal property with SmC* phase when they were dissolved (20 wt%) in achiral nematic host liquid crystal. 相似文献
926.
Masaru Watanabe Takashi Matsushita Toshiyuki Miyake 《Polymer Degradation and Stability》2009,94(12):2157-2162
Polycarbonate (PC) could be completely decomposed into its monomer, bisphenol A (BPA) with high pressure (not atmospheric pressure) high temperature steam (573 K) in 5 min reaction time. The maximum yield of BPA was about 80 mol% based on the starting PC. PC decomposition at 573 K in liquid water phase near the saturated pressure for the comparison. For 30 min in reaction in liquid water at 573 K residual PC still remained and the BPA yield was about 50% as maximum. 相似文献
927.
928.
When plasmodia of the true slime mold Physarum were exposed to unfavorable conditions presented as three consecutive pulses at constant intervals, they reduced their locomotive speed in response to each episode. When the plasmodia were subsequently subjected to favorable conditions, they spontaneously reduced their locomotive speed at the time when the next unfavorable episode would have occurred. This implied the anticipation of impending environmental change. We explored the mechanisms underlying these types of behavior from a dynamical systems perspective. 相似文献
929.
Toshiyuki Tamai Mitsuru Watanabe Tomohiro Teramura Noboru Nishioka Kimihiro Matsukawa 《Macromolecular Symposia》2010,288(1):104-110
Summary: Polymer particles decorated with metal nanoparticles were prepared by UV-irradiation of polystyrene latex particles incorporating polymethylphenylsilane (PS/PMPS) and P[S-co-NIPAM]/PMPS particles (NIPAM: N-isopropyl acrylamide) in the presence of metal salts. The metal nanoparticle/polymer hybrid particles were used as a catalyst for the reduction of 4-nitrophenol with NaBH4. The Pd- and Ag-P(S-co-NIPAM)/PMPS hybrid particles had larger metal nanoparticles and the lower catalytic activity than those of Pd- and Ag-PS/PMPS, respectively. The surface functional group of the polymer particles affected the formation of the metal nanoparticles and their catalytic activity. 相似文献
930.
Toshiyuki Kohno Hiroshi Niki 《Journal of Computational and Applied Mathematics》2010,233(9):2413-2421
Wen Li (J. Comput. Appl. Math., 182 (2005) 81-90) asserted that there are some errors in article by Hiroshi Niki, Kyouji Harada, Munenori Morimoto and Michio Sakakihara (J. Comput. Appl. Math., 164-165 (2004) 587-600). And Li presented a new proof for the corresponding results in H. Niki et al. In this paper, we point out some errors in Li’s assertion. Moreover, we show that a new proof presented by Li is imperfect. 相似文献