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41.
Molecular dynamics simulations have been performed to examine the thermodynamic properties of methane/water interface using two different water models, the TIP4P/2005 and SPC/E, and two sets of combining rules. The density profiles, interfacial tensions, surface excesses, surface pressures, and coexisting densities are calculated over a wide range of pressure conditions. The TIP4P/2005 water model was used, with an optimized combining rule between water and methane fit to the solubility, to provide good predictions of interfacial properties. The use of the infinite dilution approximation to calculate the surface excesses from the interfacial tensions is examined comparing the surface pressures obtained by different approaches. It is shown that both the change of methane solubilities in pressure and position of maximum methane density profile at the interface are independent of pressure up to about 2 MPa. We have also calculated the adsorption enthalpies and entropies to describe the temperature dependency of the adsorption. 相似文献
42.
Yoshida H Ito Y Yoshikawa Y Ohshita J Takaki K 《Chemical communications (Cambridge, England)》2011,47(30):8664-8666
Trifluoromethyl ketones were found to be coupled with arynes in three modes depending upon their substitution patterns, namely C-C bond cleavage, [2+2] cycloaddition and O-arylation. 相似文献
43.
Dr. Yasuhiro Yamashita Takaki Imaizumi Dr. Xun‐Xiang Guo Prof. Dr. Shū Kobayashi 《化学:亚洲杂志》2011,6(9):2550-2559
Asymmetric [3+2] cycloaddition of α‐aminoester Schiff bases with substituted olefins is one of the most efficient methods for the preparation of chiral pyrrolidine derivatives in optically pure form. In spite of its potential utility, applicable substrates for this method have been limited to Schiff bases that bear relatively acidic α‐hydrogen atoms. Here we report a chiral silver amide complex for asymmetric [3+2] cycloaddition reactions. A silver complex prepared from silver bis(trimethylsilyl)amide (AgHMDS) and (R)‐DTBM‐SEGPHOS worked well in asymmetric [3+2] cycloaddition reactions of α‐aminoester Schiff bases with several olefins to afford the corresponding pyrrolidine derivatives in high yields with remarkable exo‐ and enantioselectivities. Furthermore, α‐aminophosphonate Schiff bases, which have less acidic α‐hydrogen atoms, also reacted with olefins with high exo‐ and enantioselectivities. The stereoselectivities of the [3+2] cycloadditions with maleate and fumarate suggested that the reaction proceeded by means of a concerted mechanism. An NMR spectroscopic study indicated that complexation of AgHMDS with the bisphosphine ligand was not complete, and that free AgHMDS, which did not show any significant catalytic activity, existed in the catalyst solution. This means that significant ligand acceleration occurred in the current reaction system. 相似文献
44.
Chikara Shito Keitaro Okamoto Yuki Sato Ryuji Watanabe Tomonori Ohashi Kazuhiro Fuchizaki 《高压研究》2013,33(3):499-508
ABSTRACTHigh pressure hydrous phases with distorted rutile-type structure have attracted much interest as potential water reservoirs in the Earth’s mantle. An in-situ X-ray diffraction study of β-CrOOH was performed at high pressures of up to 6.2?GPa and high-temperatures of up to 700?K in order to clarify the temperature effect on compression behaviors of β-CrOOH. The P-V-T data fitted to a Birch–Murnaghan equation of state yielded the following results: isothermal bulk modulus KT0?=?191(4)?GPa, temperature derivative (?KT/?T)P?=??0.04(2)?GPa?K?1, and volumetric thermal expansion coefficient α?=?3.3(2)?×?10?5?K?1. In this study, at 300?K, the a-axis became less compressible at pressures above 1–2?GPa. We found that the pressure where the slopes of a/b and a/c ratios turned positive increased with temperature. This is the first experimental study indicating the temperature dependence of the change in the axial compressibility in distorted rutile-type M3+OOH. 相似文献
45.
Ryuji Kajikiya 《Journal of Differential Equations》2002,186(1):299-343
We deal with sublinear elliptic equations in a ball and prove the existence of infinitely many solutions which are not radially symmetric but G invariant. Here G is any closed subgroup of the orthogonal group and is not transitive on the unit sphere. 相似文献
46.
The power spectral density function (PSDF) of the log-amplitude scintillation for an infrared laser beam was measured experimentally. To investigate the contribution of the absorption and the dispersion that cause the scintillation, we chose 16 wavelengths of infrared light and one wavelength of visible light. It is found that the spectral density of scintillation for the infrared beam does not agree with that for the visible beam, as predicted by Tatarskii's theory in the low-frequency region below 1 Hz. This disagreement between the experiment and the theory in the low-frequency region should be attributed to water vapour absorption. 相似文献
47.
To deal with the radiation from an axially symmetric pillbox resonator embedded in LiNbO3 substrate, an eigenvalue equation is derived from the expression of the finite-element beam propagation method in a cylindrical coordinate system. By solving the eigenvalue equation iteratively, the field distributions and the angular phase constants of the pillbox resonator are evaluated. The iterative scheme of solving the eigenvalue equation is an extension of our previous direct solution method which was described for a lossless case. The results obtained by this method are compared with those obtained analytically, and excellent agreement is found. 相似文献
48.
Sugi R Yokoyama A Furuyama T Uchiyama M Yokozawa T 《Journal of the American Chemical Society》2005,127(29):10172-10173
The polycondensation of m-(octylamino)benzoic acid esters (1) with base was investigated in order to extend the synthesis of well-defined condensation polymers from para-substituted polymers to meta-substituted ones. We expected that the aminyl anion of 2 would deactivate the ester moiety at the meta position of 2 owing to the strong inductive effect of the anion, resulting in, not self-polycondensation, but chain-growth polycondensation. The methyl ester monomer 1a polymerized with lithium hexamethyldisilazide (LiHMDS) in the presence of phenyl benzoate (3a) as an initiator at 0 degrees C to afford a polymer with a low polydispersity, but the product contained a small amount of self-condensation polymer. On the other hand, the polymerization of the ethyl ester monomer (1b) with phenyl 4-methylbenzoate (3b) proceeded through chain polymerization without self-polycondensation. The Mn values of the polymers increased linearly in proportion to the [1b]0/[3b]0 ratio, and the Mw/Mn ratios remained narrow over the entire [1b]0/[3b]0 range. Furthermore, a block copolymer of N-alkylated poly(m-benzamide) and poly(p-benzamide) with a low polydispersity was synthesized by the monomer addition method under this polymerization condition. 相似文献
49.
Komeyama K Sasayama D Kawabata T Takehira K Takaki K 《Chemical communications (Cambridge, England)》2005,(5):634-636
Rare-earth silylamide complexes, Ln[N(SiMe3)2]3 (Ln = Y, La, Sm, Yb), effectively catalyzed the coupling reaction of isocyanides with both aliphatic and aromatic terminal alkynes under mild conditions. 相似文献
50.