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91.
Noguchi H Kondoh A Hattori Y Kanoh H Kajiro H Kaneko K 《The journal of physical chemistry. B》2005,109(29):13851-13853
We measured adsorption and desorption isotherms of methane on [Cu(4, 4'-bipyridine)2(BF4)2] (LPC) at 258, 273, and 303 K. Adsorption proceeds almost vertically at a definite pressure, which is named gate pressure. The lower the measurement temperature, the smaller the gate pressure. The temperature dependence of the gate pressure is expressed by the Clapeyron-Clausius equation, giving a thermodynamic evidence on the clathrate formation between the Cu complex and methane. 相似文献
92.
Wormlike micelles of nonionic surfactants pentaoxyethylene decyl ether C(10)E(5) and hexaoxyethylene decyl ether C(10)E(6) in dilute aqueous solutions were characterized by static (SLS) and dynamic light scattering (DLS) experiments at several temperatures T below the critical points. The SLS results were analyzed with the aid of the molecular thermodynamic theory for SLS from micelle solutions formulated with the wormlike spherocylinder model, thereby yielding the molar mass M(w) of the micelles as a function of c and the cross-sectional diameter d of 2.6 nm for both C(10)E(5) and C(10)E(6) micelles. It has been found that the micelles grow in size with increasing c and T, following the relation M(w) proportional, variant c(1/2) in conformity with the theoretical prediction for highly extended polymerlike micelles. The hydrodynamic radius R(H) of the micelles as a function of M(w) was found to be also well described by the corresponding theories for the wormlike spherocylinder model. The results of the stiffness parameter lambda(-1) show that both micelles are rather stiff compared with those formed with other polyoxyethylene alkyl ethers C(i)E(j) but far from rigid rods. The values of the spacing s between two adjacent hexaoxyethylene chains on the micellar surface were found to be substantially the same for both micelles. 相似文献
93.
Shinohara Y Kawasaki N Ueno S Kobayashi I Nakajima M Amemiya Y 《Physical review letters》2005,94(9):097801
Crystallization of n-hexadecane in emulsion droplets was studied using time-resolved two-dimensional small- and wide-angle x-ray scattering with differential scanning calorimetry (2D-SAXS-WAXS-in situ DSC) which provides information about both nano- and subnanoscale structural change. n-hexadecane in droplets reproducibly crystallized into the stable triclinic phase via a transient-rotator phase. This is in contrast with previous results that the rotator phase of n-hexadecane was observed only occasionally for bulk samples. Thus we confirmed the existence of rotator phase in n-hexadecane, which is important for the study of crystallization of soft materials. We suggest that the rotator phase at the interface of oil and water plays a precursor role for bulk crystallization. This study demonstrates that 2D-SAXS-WAXS-in situ DSC is a powerful tool for the study of a transient phase. 相似文献
94.
Numao N Fujii H Fukazawa Y Hanagata N Tanaka K 《Chemical & pharmaceutical bulletin》2004,52(3):377-379
In the sequence Fourier analysis (SFA) of specific interactions such as those between fibroblast growth factors (FGFs)/FGF receptors (FGFRs), bone morphogenetic proteins (BMPs)/BMP receptors (BMPRs), or tumor repressor protein p53/mouse double minute 2 homolog (MDM2), the characteristic frequency peak(s) could be observed with the hydrophobic scale for 20 amino acids as well as 4 nucleotides as the physicochemical parameter, but not successfully with the absolute electronegativity scale. This result implies that these two independent scales should be appropriately selected in various specific ligand-protein interactions, though the critical difference has to be determined. 相似文献
95.
Hongo K Maezono R Kawazoe Y Yasuhara H Towler MD Needs RJ 《The Journal of chemical physics》2004,121(15):7144-7147
Hund's multiplicity rule is investigated for the carbon atom using quantum Monte Carlo methods. Our calculations give an accurate account of electronic correlation and obey the virial theorem to high accuracy. This allows us to obtain accurate values for each of the energy terms and therefore to give a convincing explanation of the mechanism by which Hund's rule operates in carbon. We find that the energy gain in the triplet with respect to the singlet state is due to the greater electron-nucleus attraction in the higher spin state, in accordance with Hartree-Fock calculations and studies including correlation. The method used here can easily be extended to heavier atoms. 相似文献
96.
97.
98.
Ohki Y Sunada Y Honda M Katada M Tatsumi K 《Journal of the American Chemical Society》2003,125(14):4052-4053
The [8Fe-7S] core of the P-clusters in nitrogenases is unique among the known [Fe-S] clusters which are essential to electron-transfer processes in nature. The [8Fe-7S] cluster has been thought unstable and to exist only in protein environments. We found that this unusual [8Fe-7S] structure can be self-assembled from the reaction of Fe(II) bis-amide, tetramethylthiourea, 2,4,6-triisopropylbenzenethiol, and elemental sulfur in a specific mole ratio. The structure of the complex isolated therefrom closely resembles that of the reduced form (PN) of the P-clusters, while the 6Fe(II)2Fe(III) oxidation state was manifested by the M?ssbauer study. 相似文献
99.
The rotational spectrum of the deuterated isopropanol (CH(3))(2)CHOD has been observed by Fourier transform microwave spectroscopy and analyzed to yield tunneling splitting of 4431.4613 (17) MHz, between the antisymmetric and the symmetric gauche forms, which is much larger than the 2400 MHz estimated from the internal-rotation potential function reported in the literature. The potential function for the OH internal rotation has been examined in view of the discrepancy between the observed and estimated tunneling splitting, and it was accounted for by taking into account isotope effects on the potential constants. The deuterium quadrupole coupling effect has been included together with the Coriolis terms in the off-diagonal block of the Hamiltonian matrix for the gauche form. The deuterium quadrupole coupling constants obtained for the trans form were employed to calculate the components of the coupling constants as functions of the internal-rotation angle, and the components at around 120 degrees were compared with the values observed for the gauche form, thereby leading to unambiguous determination of the signs of the constants in the off-diagonal block; the signs are not obtainable from an ordinary analysis of the rotational spectra. The chirality of the gauche form was discussed by placing special emphasis on the effect of intermolecular interactions between two chiral molecules. Copyright 2001 Academic Press. 相似文献
100.
Within the methodology [M. Khazaei, A.A. Farajian, Y. Kawazoe, Phys. Rev. Lett. 95 (2005) 177602] based on first-principles electronic structure calculations, the effects of Cs treatment on current emissions and emission patterns of capped carbon nanotubes are considered at low deposition densities when the nanotubes are under an electric field 0.2 V/Å. The results show that the current emission from the cap with one adsorbed Cs is 3.4 times larger than the cap without any Cs. It is 9.6 times larger in the cap with two adsorbed Cs atoms. After Cs deposition the emission patterns become asymmetric (current emission from the carbon atoms located at the topmost pentagon ring close to Cs atoms is larger than the other atomic sites). There are very few localized states on Cs atoms. Hence, although the tunneling probability of electron emission from Cs atoms is significant, there is no current from Cs atoms. In addition, the effect of Cs on work function reduction of nanotubes is explained in terms of Cs deposition densities and the surface dipole moments. 相似文献