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991.
Tsutomu Kimura Takahiro Tsuru Hitoshi Momochi Tsuyoshi Satoh 《Heteroatom Chemistry》2013,24(2):131-137
Racemization of optically active dichloromethyl p‐tolyl sulfoxide took place at −78°C in the presence of potassium bis(trimethylsilyl)amide (KHMDS), while the same racemization did not occur under reflux in toluene in the absence of KHMDS. Density functional theory calculations suggested that the pyramidal inversion at the sulfur center was unlikely to be involved in the racemization mechanism. An anionic species of the sulfoxide was found to be gradually converted into chlorobis(p‐tolylsulfinyl)methane and dichlorocarbene. We propose a racemization mechanism mediated by achiral potassium p‐toluenesulfenate and chloro(p‐tolylsulfinyl)methylene. © 2013 Wiley Periodicals, Inc. Heteroatom Chem 24:131–137, 2013; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.21074 相似文献
992.
A sum rule treatment using Hall's equivalent orbitals has been applied to the valence orbital ionization energies of mono-, di- and trimethylamine up to about 40 eV assuming Koopman's theorem. Excellent agreement is obtained between theory and experiment in partial and total energy sums. A similar treatment using p-type localized orbitals previously proposed by the authors is also applied to ionization energies below about 18 eV for the methyl amines. In these sum rule treatments we use both the vertical ionization energies obtained from He (I) photoelectron spectra measured here and the higher ionization energies deduced from the He (II) photoelectron spectra published by Potts et al. The complete sets of valence orbital ionization energies of the methyl amines have thus been identified by sum rule considerations in photoelectron spectroscopy. We show that the character of the corresponding MO's may be inferred from the sum rule. The orbital orderings and characters of the methyl amines have also been studied by CNDO/2 and MINDO/2 methods. 相似文献
993.
Hideaki Ishihara Itsuro Kimura Nori Yoshihara 《Journal of Macromolecular Science: Physics》2013,52(5-6):713-733
Structure studies on the segmented polyurethane-urea based on poly(tetramethylene glycol), 4,4'-diphenylmethane diisocyanate, and 4,4'-diaminodiphenylmethane have been made using wide- and small-angle x-ray diffraction. It was found that the hard segments have a well-defined crystal structure indexed by a monoclinic unit cell with dimensions a = 4.72 Å, b = 11.33 Å, c (chain axis) = 11.64 Å, and γ = 116.5°. Further, the hard segments have an anisotropic supermolecular structure, that is, a spherulitic crystalline texture. The microdomain structure depends on the molecular weight of the soft segments, with phase separation becoming distinct with an increase in the molecular weight of the soft segment. Based on the long period observed in small-angle x-ray patterns of heat-set specimens, the thickness of lamellae was estimated to be about 93 Å. This corresponds to an average hard segment sequence length of 8. On deformation, the hard segment orients preferably transverse to the stretch direction up to high elongations, and it shows a hysteresis of orientation. This phenomenon can be explained in terms of the anisotropic supermolecular structure. Further, deviation from ideal rubber elasticity observed in the stress-strain relationships of the segmented polyure-thane-urea elastomers might also be caused by the anisotropic structure. 相似文献
994.
We will give quiver presentations of the Grothendieck constructions of functors from a small category to the 2-category of 𝕜-categories for a commutative ring 𝕜. 相似文献
995.
Let G be a finite graph on the vertex set [d] = {1,…, d} with the edges e 1,…, e n and K[t] = K[t 1,…, t d ] the polynomial ring in d variables over a field K. The edge ring of G is the semigroup ring K[G] which is generated by those monomials t e = t i t j such that e = {i, j} is an edge of G. Let K[x] = K[x 1,…, x n ] be the polynomial ring in n variables over K, and define the surjective homomorphism π: K[x] → K[G] by setting π(x i ) = t e i for i = 1,…, n. The toric ideal I G of G is the kernel of π. It will be proved that, given integers f and d with 6 ≤ f ≤ d, there exists a finite connected nonbipartite graph G on [d] together with a reverse lexicographic order <rev on K[x] and a lexicographic order <lex on K[x] such that (i) K[G] is normal with Krull-dim K[G] = d, (ii) depth K[x]/in<rev (I G ) = f and K[x]/in<lex (I G ) is Cohen–Macaulay, where in<rev (I G ) (resp., in<lex (I G )) is the initial ideal of I G with respect to <rev (resp., <lex) and where depth K[x]/in<rev (I G ) is the depth of K[x]/in<rev (I G ). 相似文献
996.
Misato Kazama Hiroshi Shinotsuka Takashi Fujikawa Mauro Stener Piero Decleva Jun-ichi Adachi Tomoya Mizuno Akira Yagishita 《Journal of Electron Spectroscopy and Related Phenomena》2012
1s photoelectron angular distributions from fixed-in-space CO2, NO2, BF3 and CH3F molecules have been calculated by X-ray photoelectron diffraction (XPD) theory with muffin-tin-type molecular potential. For all the molecules, the calculated results show good agreements with those by density functional theory in the energy region ?100 eV. Furthermore, for all the molecules experimental data on the angular distributions in such energy region are well reproduced by the XPD theory. These intensive studies lead to a rather general rule that the XPD theory is an adequate tool to describe high-energy photoelectron angular distributions for any single oriented molecules. 相似文献
997.
Shigefumi Kimura Pleiades Tiharu Inaoka Toshiaki Yamazaki 《Physical Therapy Research》2012,15(1):9-14
The purpose of this study was to determine the influence of passive stretching on inhibition of disuse atrophy and hemodynamics among longitudinal regions of the rat soleus muscle. Disuse muscle atrophy was induced by hindlimb suspension for two weeks. Muscle blood flow was evaluated using thallium-201 (201Tl) which is a radiotracer that has been reported to be useful to assess blood perfusion in skeletal muscle. Thirty-nine male Wistar rats were divided randomly into 5 groups: control (C: n = 10), a group with hindlimb suspension (HS: n = 7), a group with hindlimb suspension and stretching (ST: n = 7), a group receiving only a single session of stretching after the hindlimb suspension period that was killed just after stretching (HSB: n = 7), and a group receiving only a single session of stretching hindlimb suspension and stretching period that was killed just after stretching (STB: n = 8). From the results of the cross-sectional area (CSA) and the capillary-to-fiber ratio (C/F), muscle atrophy and inhibition of atrophy were shown more in proximal than in distal regions of experimental groups. These results suggest that the alterations of the C/F and CSA were different among muscle regions in experimental groups. These differences may depend on the level of stretching. Moreover, alteration of blood flow resulting from alteration of the mechanical environment had little influence on muscle atrophy or inhibition of atrophy. 相似文献
998.
The subnanometer topography of a partially crystalline polyethylene film was observed in liquid n-dodecane using a frequency-modulation atomic force microscope. Locally ordered structures were found and assigned to a (100) facet of crystalline domains. 相似文献
999.
Machida Y Itoh A So Y Izawa K Haga Y Yamamoto E Kimura N Onuki Y Tsutsumi Y Machida K 《Physical review letters》2012,108(15):157002
The field-orientation dependent thermal conductivity of the heavy-fermion superconductor UPt3 was measured down to very low temperatures and under magnetic fields throughout the distinct superconducting phases: B and C phases. In the C phase, a striking twofold oscillation of the thermal conductivity within the basal plane is resolved reflecting the superconducting gap structure with a line of node along the a axis. Moreover, we find an abrupt vanishing of the oscillation across a transition to the B phase, as a clear indication of a change of gap symmetries. We also identify extra two line nodes below and above the equator in both B and C phases. From these results together with the symmetry consideration, the gap function of UPt3 is determined as a E(1u) representation characterized by a combination of two line nodes at the tropics and point nodes at the poles. 相似文献
1000.
Large eddy simulations of turbulent flow between shrouded co-rotating disks, representing a simplified model of a hard disk drive, are performed. The computation domain surrounds a complete disk and is bounded at top and bottom by half a disk. Therefore, it is possible to compute the fluctuating pressure field surrounding the middle disk. Also, the influence of the shroud geometry is taken into account by comparing a flat shroud wall and a wall with rib chambers. In the flat shroud case, the fluctuating pressure on the upper- and lower-surface of a disk indicates a strong correlation with fluid motion travelling across the disk-tip clearance region. However, in the ribbed shroud case the organized flow structure that is observed in the flat shroud case disappears and the fluctuating pressure acting on the surface of the disk is remarkably diminished. 相似文献