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1.
Machiko Shigemi Takahiro Takekiyo Hiroshi Abe Nozomu Hamaya Yukihiro Yoshimura 《Journal of solution chemistry》2014,43(9-10):1614-1624
We have used Raman spectroscopy to investigate the high-pressure phase behavior of 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]), a representative ionic liquid, at pressures up to ~7.5 GPa. We have also studied how increasing pressure leads to conformational changes in the [bmim]+ cation. We have found that liquid [bmim][BF4] undergoes pressure-induced solidification (freezing) into a superpressed (metastable) state at 2.5 GPa; another structural change probably occurs at ~6 GPa. Remarkably, conformational changes in the [bmim]+ cation between trans and gauche conformers are concordant with the metastable structural changes of [bmim][BF4]. As the pressure is increased from ambient, the fraction of gauche conformers increases, but the gauche fraction decreases above the solidification pressure (2.5 GPa), and slope of the gauche/trans ratio changes again above 6 GPa. We interpret these results in terms of the fragility of the ionic liquid. 相似文献
2.
Susumu Tajima Yukiyoshi Nagai Osamu Sekiguchi Masao Fujishige Nozomu Uchida 《Journal of the American Society for Mass Spectrometry》1995,6(3):202-206
The spontaneous unimolecular dissociation reaction of methyl lactate (1) ionized by electron impact was investigated by a combination of mass-analyzed ion kinetic energy spectrometry and deuterium labeling. The metastable ions 1+· decompose in a variety of ways: four fragment peaks are observed at m/z 89, 76, 61, and 45, which correspond to the losses of ?H3, CO, CH3?O, and ?OOCH3, respectively. Double hydrogen atom transfer occurs in the third reaction. The source-generated m/z 61 ions decompose into oxygen-protonated methanols at m/z 33 ([CH3OH 2 + ]) by the loss of CO with double hydrogen atom migration. Both hydroxyl and methyne hydrogen atoms in 1 +· are present in the resultant protonated methanols. 相似文献
3.
Ken-Ichi Okamoto Nozomu Tanihara Hitoshi Watanabe Kazuhiro Tanaka Hidetoshi Kita Asumaru Nakamura Yoshihiro Kusuki Kanji Nakagawa 《Journal of Polymer Science.Polymer Physics》1992,30(11):1223-1231
Sorption and diffusion of water vapor are investigated gravimetrically for polyimide films. The activity dependence of the solubility and diffusion coefficients, S and D, respectively, is classified under four types: (1) constant S and D type, (2) dual-mode sorption and transport type, (3) dual-mode type followed by a deviation due to a plasticization effect at high vapor activity, and (4) constant S and D type followed by a deviation due to water cluster formation at high activity. For the dual-mode type, the Henry's law component is much larger than the Langmuir component except at low activity, and therefore deviation in behavior from the first type is small. S is larger for polyimides with higher content of polar groups such as carbonyl, carboxyl, and sulfonyl. D is larger for polyimides with a higher fraction of free space, with some exceptions. The polyimide from 3,3′,4,4′-biphenyltetracarboxylic dianhydride and dimethyl-3,7-diaminodibenzothiophene-5, 5-dioxide belongs to the third type and displays both large S and large D. The polyimide from 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride and 4,4′-oxydianiline belongs to the fourth type, and has the largest D but rather small S because of the hydrophobic C(CF3)2 groups. © 1992 John Wiley & Sons, Inc. 相似文献
4.
Gang Wei Nozomu Sasage Yusuke Kusanagi Kazuhiro Fujiki Takeshi Yamauchi Norio Tsubokawa 《Journal of polymer science. Part A, Polymer chemistry》2008,46(12):4218-4226
The surface grafting of hyperbranched cyclotriphosphazene polymer onto silica nanoparticles and carbon black was investigated. The grafting of hyperbranched cyclotriphosphazene polymer onto these surfaces was achieved by the repeated reactions of hexachlorocyclotriphosphazene with hexamethylenediamine from surface amino groups and sodium carboxylate groups, respectively. The percentage of grafting onto silica and carbon black surfaces exceeded 760 and 390%, respectively. However, it proved difficult to achieve the theoretical growth of cyclotriphosphazene polymer from these surfaces because of steric hindrance. The introduction of sulfonic acid groups was successfully achieved by the reaction of terminal chlorophosphazene groups of the hyperbranched polymer‐grafted silica and carbon black with sulfanilic acid. The content of sulfonic acid groups introduced onto silica and carbon black surfaces was 4.98 mmol/g and 5.70 mmol/g, respectively. The sulfonated cyclotriphosphazene polymer‐grafted carbon black was extremely hydrophilic, yielding stable colloidal dispersions in polar solvents. The sulfonated cyclotriphosphazene polymer‐grafted silica and carbon black showed ionic conductivity, with the conductance increasing exponentially with increasing relative humidity and temperature. This study may offer important leads in the application of silica nanoparticles and carbon black in polymeric membranes for fuel cells. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4218–4226, 2008 相似文献
5.
6.
Hiroshi Noguchi Tsuyoshi Michinobu Nozomu Fujii Masahiro Funahashi Masatoshi Tokita Junji Watanabe Kiyotaka Shigehara 《Journal of polymer science. Part A, Polymer chemistry》2008,46(15):5101-5114
Cyanotolane or fluorotolane mesogens were for the first time introduced into the fumarate monomer under basic conditions. All fumarate monomers undergo radical polymerization in benzene in the presence of dimethyl 2,2′‐azobis(isobutyrate) as an initiator at 60 °C, affording the corresponding poly(fumarate)s with a molecular weight (Mn) of ~ 104 and an exceptionally narrow polydispersity. The phase behaviors of the fumarate monomers and the correspoding poly(fumarate)s were comprehensively investigated by differential scanning calorimetry (DSC), polarized optical microscopy (POM), and X‐ray diffraction (XRD) analysis. For the fumarate monomers, fluorotolane derivatives were prone to form higher‐order liquid crystal phases such as a smectic phase, while cyanotolane derivatives tended to show a wide mesophase temperature range, depending on the alkyl chain spacer length. Very surprisingly, these features dramatically weakened when they were polymerized. The mesophase temperature ranges became narrow and completely disappeared for the poly(fumarate)s with a shorter alkyl chain spacer. A nematic phase representing lower‐order arrangements became a predominant liquid crystal phase for the poly(fumarate) carrying cyanotolane mesogens. Only the poly(fumarate) carrying fluorotolane mesogens with a longer alkyl chain spacer displayed the characteristic XRD patterns of the smectic B phase. The transient photocurrent measurements of the fumarate monomer with cyanotolane mesogens displayed a hole mobility of the order of 10?4–10?5 cm2 V?1 s?1 at room temperature. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5101–5114, 2008 相似文献
7.
Flame dynamics under various backpressures in a model scramjet with and without a cavity flameholder
Flame dynamics under various backpressure conditions were experimentally investigated using direct flame visualization, high-speed CH* chemiluminescence imaging, and wall pressure measurements. The stagnation pressure and temperature used in the present study were 100 kPa and 2500 K, respectively, with a freestream Mach number of 4.5. Rectangular scramjet models with and without a cavity were used to explore the effects of the cavity on flame dynamics when operating in scramjet mode, ramjet mode, and unstart. The flow rate of the ethylene jet was varied to impose backpressures corresponding to each operation mode. For both models, reverse flame propagation was observed for ramjet mode and unstart. For ramjet mode, flame fluctuation occurred within the isolator due to the coupling of fluid dynamics and combustion. The presence of a cavity enhanced combustion and reduced flame fluctuation in both scram and ramjet mode. The cavity promoted unstart because of the greater heat release from combustion. Further research using spatially resolved diagnostic techniques is needed to identify the flame locations for ramjet mode and unstart. 相似文献
8.
Farouq Ahmed Ryo NagumoRyuji Miura Suzuki AiHideyuki Tsuboi Nozomu HatakeyamaAkira Endou Hiromitsu TakabaMomoji Kubo Akira Miyamoto 《Applied Surface Science》2011,257(24):10503-10513
The notion of “active sites” is fundamental to heterogeneous catalysis. However, the exact nature of the active sites, and hence the mechanism by which they act, are still largely a matter of speculation. In this study, we have presented a systematic quantum chemical molecular dynamics (QCMD) calculations for the interaction of hydrogen on different step and terrace sites of the Pd (3 3 2) surface. Finally the dissociative adsorption of hydrogen on step and terrace as well as the influence of surface hydrogen vacancy for the dissociative adsorption of hydrogen has been investigated through QCMD. This is a state-of-the-art method for calculating the interaction of atoms and molecules with metal surfaces. It is found that fully hydrogen covered (saturated) step sites can dissociate hydrogen moderately and that a monovacancy surface is suitable for significant dissociative adsorption of hydrogen. However in terrace site of the surface we have found that dissociation of hydrogen takes place only on Pd sites where the metal atom is not bound to any pre-adsorbed hydrogen atoms. Furthermore, from the molecular dynamics and electronic structure calculations, we identify a number of consequences for the interpretation and modeling of diffusion experiments demonstrating the coverage and directional dependence of atomic hydrogen diffusion on stepped palladium surface. 相似文献
9.
Hidehito Nanto Fumitaka Endo Yoshiaki Hirai Shouichi Nasu Nozomu Takeuchi 《Optical Review》1994,1(2):177-179
Intense photostimulated luminescence (PSL) with a peak at 420 nm is observed in ultraviolet (UV) Iight-irradiated europium-doped potassium chloride (KCl: Eu) crystalline phosphors. The PSL characteristics of UV-irradiated KCl: Eu phosphor for optical memory application were studied. The excitation and emission mechanisms of the 420 nm PSL, which are consistent with the results obtained, are discussed. 相似文献
10.
Mg isotope fractionation in biogenic carbonates of deep-sea coral, benthic foraminifera, and hermatypic coral 总被引:1,自引:0,他引:1
Yoshimura T Tanimizu M Inoue M Suzuki A Iwasaki N Kawahata H 《Analytical and bioanalytical chemistry》2011,401(9):2755-2769
High-precision Mg isotope measurements by multiple collector inductively coupled plasma mass spectrometry were applied for
determinations of magnesium isotopic fractionation of biogenic calcium carbonates from seawater with a rapid Mg purification
technique. The mean δ26Mg values of scleractinian corals, giant clam, benthic foraminifera, and calcite deep-sea corals were −0.87‰, −2.57‰, −2.34‰,
and −2.43‰, suggesting preferential precipitation of light Mg isotopes to produce carbonate skeleton in biomineralization.
Mg isotope fractionation in deep-sea coral, which has high Mg calcite skeleton, showed a clear temperature (T) dependence from 2.5 °C to 19.5 °C: 1,000 × ln(α) = −2.63 (±0.076) + 0.0138 (±0.0051) × T(R
2 = 0.82, p < 0.01). The δ26Mg values of large benthic foraminifera, which are also composed of a high-Mg calcite skeleton, can be plotted on the same
regression line as that for deep-sea coral. Since the precipitation rates of deep-sea coral and benthic foraminifera are several
orders of magnitude different, the results suggest that kinetic isotope fractionation may not be a major controlling factor
for high-Mg calcite. The Mg isotope fractionation factors and the slope of temperature dependence from deep-sea corals and
benthic foraminifera are similar to that for an inorganically precipitated calcite speleothem. Taking into account element
partitioning and the calcification rate of biogenic CaCO3, the similarity among inorganic minerals, deep-sea corals, and benthic foraminiferas may indicate a strong mineralogical
control on Mg isotope fractionation for high-Mg calcite. On the other hand, δ26Mg in hermatypic corals composed of aragonite has been comparable with previous data on biogenic aragonite of coral, sclerosponges,
and scaphopad, regardless of species differences of samples. 相似文献