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941.
Sakai D Matsuda Y Hachiya M Mori M Fujii A Mikami N 《The journal of physical chemistry. A》2008,112(30):6840-6849
Vibrational spectroscopy of size-selected formamide-water clusters, FA-(H2O)n , n = 1-4, prepared in a supersonic jet is performed with vacuum-ultraviolet-ionization detected-infrared predissociation spectroscopy (VUV-ID-IRPDS). The cluster structures are determined through comparisons of the observed IR spectra with theoretical calculations at the MP2/6-31++G** level. The FA-(H2O)n , n = 1-3, clusters have ring-type structures, where water molecules act as both single donor and single acceptor in the hydrogen-bond network between the amino and carbonyl groups of FA. For FA-(H2O)4, on the other hand, the absence of the free NH stretching vibration indicates formation of a double ring type structure, where two NH bonds of the amino group and the carbonyl oxygen of FA form hydrogen bonds with water molecules. An infrared spectrum of the formamide-water cluster cation, [FA-H2O](+), is also observed with infrared predissociation spectroscopy of vacuum-ultraviolet-pumped ion (IRPDS-VUV-PI). No band is observed for the free OH stretches of neutral water. This shows [FA-H2O](+) has such a structure that one of the hydrogen atoms of the water moiety is transferred to the carbonyl oxygen of FA(+). 相似文献
942.
Kim S Miyakawa M Hayashi K Sakai T Hirano M Hosono H 《Journal of the American Chemical Society》2005,127(5):1370-1371
Electrides are ionic compounds in which electrons act as anions. These compounds are expected to have interesting properties arising from their exotic structure. The fatal drawbacks of the thermal and chemical instability of organic electrides were resolved by the synthesis of a room temperature (RT) stable electride using single crystalline 12CaO.7Al2O3 (C12A7) with a nanoporous structure and the chemical treatments for a long duration. However, an innovative fabrication method is obviously required for practical applications such as cold electron-emitter and thermionic devices. Herein we report a simple synthesis for polycrystalline C12A7 electrides with a moderate electronic conductivity via a strongly reducing C12A7 "melt", i.e., direct solidification of the melt or crystallization of the transparent glass. Generation of carrier electrons and precipitation of the C12A7 phase from the strongly reducing melt and glass are likely associated with the incorporation of carbon-related anions for stabilizing the C12A7 phase and keeping the mobile electrons in C12A7. These findings will be broadly utilized for applications by mass production in a desired shape and dimension, facilitating the research of electrides. 相似文献
943.
Wang T Sakai Y Nakajima K Miyawaki A Ito K Hara M 《Colloids and surfaces. B, Biointerfaces》2005,40(3-4):183-187
The force measurement mode of an atomic force microscope (AFM) has enabled us to measure the mechanical properties of biological materials at the single molecular level. In a conventional quasi-static force measurement on a single circularly permuted green fluorescent protein (cpGFP), we could unfold it by unraveling several sub-domains in a distinct sawtooth pattern at a slow stretching speed. In order to elucidate more detailed conformational changes at each extension length, we further measured dynamic relax-stress response of cpGFP molecules. In this measurement, several cycles of sinusoidal movement were applied to the sample during the stretching process. We found the protein molecule showed in-phase response to the sinusoidal input in most case of measurements. 相似文献
944.
With the non-Abelian hyper-Kähler quotient by U(M) and SU(M) gauge groups, we give the massive hyper-Kähler sigma models that are not toric in the N=1 superfield formalism. The U(M) quotient gives N!/[M!(N-M)!] (N is the number of flavors) discrete vacua that may allow various types of domain walls, whereas the SU(M) quotient gives no discrete vacua. We derive a BPS domain-wall solution in the case of N = 2 and M = 1 in the U(M) quotient model. 相似文献
945.
Hara Y Sakai T Maeda S Hashimoto S Yoshida R 《The journal of physical chemistry. B》2005,109(49):23316-23319
A new type of self-oscillating polymer was prepared by utilizing the Belousov-Zhabotinsky reaction. In this study, capture sites with a positive charge for an oxidizing agent as a counterion were incorporated into the copolymer of N-isopropylacrylamide and the ruthenium complex as a catalyst. Soluble-insoluble self-oscillation of the polymer was first achieved without adding an oxidizing agent. The effect of temperature on the self-oscillating behavior was investigated. It was clarified that the polymer had two advantageous characteristics because of the higher LCST; one is to enable self-oscillation around body temperature, and the other is to cause the oscillation for a longer time without intermolecular aggregation among the polymer chains in the reduced state. This achievement of self-oscillation of polymer chains including an oxidizing agent may lead to their practical use under oxidant-free conditions. 相似文献
946.
Rational control of enantioselectivity of lipase by site-directed mutagenesis based on the mechanism
Ema T Fujii T Ozaki M Korenaga T Sakai T 《Chemical communications (Cambridge, England)》2005,(37):4650-4651
The enantioselectivity of a Burkholderia cepacia lipase toward secondary alcohols could be both increased and decreased rationally by introducing only a single mutation on the basis of the mechanism proposed previously. 相似文献
947.
Butane-2,3-dione was activated towards nucleophilic addition of enecarbamates by a series of metal triflate complexes of a C2-symmetric diamine to give stereogenic, aldol-like, t-alcohols, a novel nickel(II) triflate complex was identified as a good catalyst for this asymmetric transformation, and an aquo nickel(II) complex was identified by XRD techniques. 相似文献
948.
Nakamura Y Inamura K Oomuro R Laurenco R Tidwell TT Nishimura J 《Organic & biomolecular chemistry》2005,3(16):3032-3038
The reactions of various aromatic diazoketones with [60]fullerene were investigated in solution (o-dichlorobenzene) or in the solid-state. Under all the conditions examined, the fulleroid with the methine proton located over a six-membered ring was obtained as a major product along with a slight amount of the other fulleroid diastereoisomer and methanofullerene. Solid-state reactions considerably enhanced the reaction efficiency with minor effects on the selectivity. The thermal isomerization and photoisomerization from fulleroids into methanofullerene were relatively slow, almost independent of substituents under the conditions examined. 相似文献
949.
Tokunaga Y Homma Y Kambe S Aoki D Sakai H Yamamoto E Nakamura A Shiokawa Y Walstedt RE Yasuoka H 《Physical review letters》2005,94(13):137209
In order to elucidate the nature of the exotic ordered phase of NpO2 below T(0)=26 K, we have initiated the first 17O-NMR measurements on this system. From the 17O-NMR spectrum, the occurrence of two inequivalent oxygen sites has been confirmed below T0. It has also been shown that the characteristic features of the hyperfine interaction at the oxygen sites are well explained by invoking a hyperfine interaction with field-induced antiferromagnetic moments which appear as a result of the triple-q antiferroquadrupolar order. The NMR findings strongly support the occurrence of the longitudinal triple-q multipole structure in NpO2. 相似文献
950.
To understand the distinction between the effects of zwitterionic, anionic, and cationic l-leucine upon adsorption and lateral interactions at air/water surface, the surface tensions of aqueous solutions of l-leucine-l-leucine hydrochloride and l-leucine-sodium l-leucinate mixtures were measured as a function of concentration and composition at 25 degrees C. The surface activity decreases in the order l-leucine >l-leucine hydrochloride > sodium l-leucinate. Both l-leucine hydrochloride and sodium l-leucinate form gaseous adsorbed films through the experimentally accessible concentration range, while the adsorbed film of zwitterionic l-leucine shows a transition between gaseous and expanded film. 相似文献