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11.
Attractive interactions between a thiocarbonyl group and a pyridinium nucleus, and between a carbonyl group and a pyridinium nucleus have been proven by (1)H and (13)C NMR studies, UV-vis spectral analyses, and X-ray crystallographic analyses of nicotinic amides 1 and 3, and pyridinium salts 2 and 4. Comparison of the Deltadelta values, which are the differences in the chemical shifts with reference compounds 5 or 6, showed that the absolute Deltadelta values of 2 and 4 are much larger than those of 1 and 3. In the UV-vis spectra, the n-->pi absorption of the C=S group of 2a exhibited a significant blue shift in CHCl(3). X-ray crystallographic analysis of 1-4 clearly showed that the C=S group of 2a and the C=O group of 4 are very close to the pyridinium moiety compared to the case of 1 and 3. In addition, the X-ray crystal packing structure of 2a showed the C=S group is sandwiched between two pyridinium rings. These experimental results strongly suggested the existence of attractive (C=S)...Py(+) and (C=O)...Py(+) interactions in solution and in crystal. The optimized geometries of 1 and 2 calculated at the HF/6-311G level are in good agreement with their X-ray geometries. MP2/6-311G calculations for the model systems of pyridinium salts 2 and 4 predicted that the electrostatic and induction energies are the major source of the attractive interactions. Since the larger contribution of electrostatic and induction interactions are characteristic features of cation-pi interactions, the (C=S)...Py(+) and (C=O)...Py(+) interactions would be classified as a cation-pi interaction. 相似文献
12.
Stephanie L. Brock Tomoko Shimojo Steven L. Suib Yuji Hayashi Hiroshige Matsumoto 《Research on Chemical Intermediates》2002,28(1):13-24
Methane conversions of 11.9%, yields of hydrogen as high as 23.3% and energy yields of 1.0 mol H2/kWh have been achieved from CO2 reforming of CH4 in non-thermal, atmospheric pressure plasma reactors with Pt coated electrodes. Two reactors have been studied. A novel fan type reactor consisting of a movable rotor and immobile stator produced the highest yields in contrast to a tube type (silent discharge) reactor with a glass dielectric barrier. Conversions, yields of hydrogen and energy yields (expressed as mol H2/kWh) were studied for CO2/CH4 concentrations of 1.1% and 5.0% in He as a function of flow rate and input voltage. Hydrogen yields are observed to increase as the input voltage is increased from 411 V to 911 V and the flow rate is decreased from 100 cc/min to 30 cc/min. Energy yields vary only slightly with input voltage and flow rate. Hydrogen yields show little dependence on CO2/CH4 concentrations, but energy yields are approximately five times greater for the 5.0% mixture than the 1.1% mixture. Selectivities to H2, CO, coke, and low molecular weight hydrocarbons were also evaluated and compared to data obtained without CO2 in the feed. Hydrogen selectivities of nearly 100% were obtained, with small amounts of ethane and propane as the only observed side products and the selectivites were approximately the same whether CO2 was present or absent in the mixture. However, the reaction proceeds much more cleanly when CO2 is present, producing CO. The syngas product has an H2 : CO ratio of 1.5 with the fan type reactor and 0.67 with the tubular reactor. In the absence of CO2, coke is the main carbonaceous product. Under all conditions studied the fan type reactor demonstrated higher methane conversions (up to 11.9%) and selectivities to hydrogen. 相似文献
13.
Shin-ichi Hirano Toshinobu Yogo Wataru Sakamoto Seiji Yamada Tomoyuki Nakamura Tomoe Yamammto Hiroyuki Ukai Kouichi Banno Tomoko Nakafuku Yukari Ando 《Journal of Sol-Gel Science and Technology》2003,26(1-3):35-41
Nano sized crystalline particles/polymer hybrids were synthesized form designed metal-organic precursors. The newly developed method is composed of the synthesis of organic matrix by polymerization and the in situ nucleation and growth of crystalline oxide particles in the organic matrix below 100°C. The design of metal-organic precursor modified with polymerizable ligand and the selection of reaction conditions does influence the size and crystallinity of ceramic particles in organic matrix. The nano-sized magnetic particle/polymer hybrid exhibits the interesting feature of superparamagnetism and quantum size effect. The crystalline particles of BaTiO3/, PbTiO3/, and KNbO3/polymer hybrids behave to be dielectric and show the typical electro-rheological behavior. 相似文献
14.
Kenjiro Hattori Tomoko Takeuchi Mika Ogata Ayumi Takanohashi Katsuhiko Mikuni Katsuyoshi Nakanishi Hideo Imata 《Journal of inclusion phenomena and macrocyclic chemistry》2007,57(1-4):339-342
We obtained the association constants Ka of estrogen (E2) and environmental chemicals by the surface plasmon resonance (SPR) assay using the immobilized mono-6-O-α-maltosyl-β-CD (G2βCD) compared with the immobilized β-CD and the immobilized estrogen receptor (ER). The association behavior of G2βCD was shown as a ER model compound. The calibration curve was determined by the initial rate of association depending on
the various concentrations, and the minimum detectable concentrations in the order of parts per billion were calculated. The
SPR assay has advantages that the pre-treatment of the sample is not necessary and the immobilized ligand is stable and useful
for the repeated measurement. 相似文献
15.
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
16.
We apply the singular value decomposition to compress the degrees of freedom of T3 amplitude for the CCSDT-1 method (compressed CCSDT-1). This method enables us to make the number of the T3 amplitudes less than that of the T2 amplitudes, making CCSDT-1 calculations much less expensive without losing accuracy. We perform test calculations on some atoms and molecules to investigate the applicability of this method. Computational results for the electronic energies as well as timings of these calculations are presented. 相似文献
17.
Tomoko Nii Akira Takamura Kiminori Mohri Fumiyoshi Ishii 《Colloids and surfaces. B, Biointerfaces》2003,27(4):436-332
We examined hydrogenated purified egg yolk lecithins, having practical advantages over non-hydrogenated ones, as liposomal membrane materials. Liposomes were prepared by the microencapsulation vesicle (MCV) method in which liposomes are formed through two-step emulsification and dispersion. Three types of purified egg yolk lecithins with different iodine values were examined after being dissolved in one of three lipid solvents. The liposome size increased as the temperature during the second emulsification increased, being closer to the boiling temperature of the solvent. The preparation temperature in relation to the transition temperature of each lecithin was also a factor affecting liposome sizes. As for the encapsulation efficiencies of the model compound calcein in liposomes, they differed mainly depending on the solubility of each lecithin in a lipid solvent and it was more obvious in hydrogenated lecithins. A high preparation temperature resulted in lower encapsulation efficiencies, suggesting that leakage of encapsulated calcein was facilitated at high temperature in the MCV methods. There was a significant correlation between liposome sizes and encapsulation efficiencies in non-hydrogenated purified egg yolk lecithin but not in hydrogenated ones. When using hydrogenated purified egg yolk lecithins as liposomal membrane materials, it was suggested that a lipid solvent should be chosen so that a lecithin completely dissolves under the preparation condition in order to achieve a higher encapsulation efficiency. Smaller liposome particles were obtained when the second emulsification was performed at a lower temperature compared with the boiling point of the lipid solvent. These findings can be applied to control encapsulation efficiencies and particle sizes in each particular liposome preparation enclosing therapeutic agents. 相似文献
18.
19.
Kyoji Tsubakiyama Togoro Matsuo Takashi Sasaki Kenzo Yoshida Takashi Fujimura Kunio Araki 《Journal of polymer science. Part A, Polymer chemistry》1979,17(1):173-184
γ-Ray-induced polymerizations of ferrocenylmethyl methacrylate (FMMA) in crystalline and amorphous states were investigated with kinetical and ESR methods. In the crystalline state the polymerization of FMMA proceeded slowly and gave low-molecular-weight polymers, whereas in the amorphous state it proceeded rapidly and gave polymers of much higher molecular weight. Molecular weight distributions of these polymers were binodal. The temperature dependence and the dose-rate dependence of the polymerization rates were different between the two states. Wide-line nuclear magnetic resonance (NMR) spectra of the amorphous monomer suggested that the polymerization proceeded in a supercooled state. Electron spin resonance (ESR) spectra of γ-irradiated FMMA and 1,1′-ferrocenyl-di(methyl methacrylate) showed that ferrocene radicals and methacrylic radicals were formed simultaneously at low temperature; with increasing temperature the former radicals disappeared, whereas the latter changed into growing chain radicals. The yields of radicals were relatively low; this means that ferrocene groups in the monomers behave as a radiation energy absorber. 相似文献
20.
Okihiro Sugihara Tomoyuki Hirama Hisashi Fujimura Naomichi Okamoto 《Optical Review》1996,3(3):150-152
Thin film waveguides of germanosilicate glass are fabricated byrf-sputtering. Second-order nonlinearity ofd 33=3.2 pm/V is obtained from electrically poled film, and the lifetime of the nonlinearity is found to be310 years. The poled channel-waveguide is prepared and the Cerenkov-type phase-matched frequency doubling is successfully observed. 相似文献