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1.
    
The diversity of products in the reaction of diethyl azodicarboxylate (DEAD)/diisopropyl azodicarboxylate (DIAD) and activated acetylenes with PIII compounds bearing oxygen or nitrogen substituents is discussed. New findings that are useful in understanding the nature of intermediates involved in the Mitsunobu reaction are highlighted. X-ray structures of two new compounds (2-t-Bu-4-MeC6H3O)P (μ-N-t-Bu)2P+[(NH-t-Bu)N[(CO2]-i-Pr)(HNCO2-i-Pr)]](Cl-)(2-t-Bu-4-MeC6H3OH)(23)and [CH2(6-t-Bu-4-Me-C6H2O)2P(O)C(CO2Me)C-(CO2Me)CClNC(O)Cl] (33) are also reported. The structure of23 is close to one of the intermediates proposed in the Mitsunobu reaction.  相似文献   
2.
Unique crystallization and melting behavior in poly(aryl ether ketone ketone) containing alternated terephthalic and isophthalic moieties were studied by time-resolved synchrotron x-ray methods. Recently, this material has been shown to exhibit three polymorphs (forms I, II, and III). In this work, we further investigated their distinctive thermal properties and found that form I is the dominating and the most thermally stable phase while form II is favored by fast nucleation conditions and is the least stable phase. On the other hand, form III represents a minor intermediate phase that usually coexists with form I and can be transferred from form II and to form I. Structural and morphological changes in form I have been followed by simultaneous wide-angle x-ray diffraction (WAXD)/small-angle x-ray scattering (SAXS) measurements during cold- or melt-crystallization and subsequent melting. In all cases, a larger dimensional change was found in the crystallographic a-axis than the b-axis during heating and cooling. This may be due to the greater lateral stress variation with respect to temperature along the a direction of the primary lamellae which is induced by either the formation of secondary lamellae or the preferential chain-folding direction in poly(aryl ether ketone ketone)s. During the phase transitions of form II ← III in the cold-crystallized specimen and form III ← I in the melt-crystallized samples, lamellar variables (long period, lamellar thickness, and invariant) obtained from SAXS remain almost constant. This indicates that the density distribution in the long spacing is independent of the melting in form II or III. For melt-crystallization, the corresponding changes in unit-cell dimensions and lamellar morphology during the annealing-induced low endotherm are most consistent with the argument that these changes are due to the melting of thin lamellar population. © 1995 John Wiley & Sons, Inc.  相似文献   
3.
The solid-state 15N CP/MAS NMR spectra and 15N spin-lattice relaxation times (T1) of doped and dedoped 15N-labeled polypyrroles prepared by electrochemical polymerization, have been measured by means of high-resolution solid-state 15N NMR. The 15N signal of polypyrrole consists of four peaks decomposed by line shape analysis. The four peaks obtained have been assigned to the various structures of polypyrrole. Further, the half-width of the 15N NMR spectra of polypyrroles is discussed as related to the electrical conductivity. © 1995 John Wiley & Sons, Inc.  相似文献   
4.
Disordered Sr2FeMoO6 shows a drastic reduction in saturation magnetization compared to highly ordered samples, moreover magnetization as a function of the temperature for different disordered samples shows qualitatively different behaviours. We investigate the origin of such diversity by performing spatially resolved photoemission spectroscopy on various disordered samples. Our results establish that extensive electronic inhomogeneity, arising most probably from an underlying chemical inhomogeneity in disordered samples, is responsible for the observed magnetic inhomogeneity. It is further pointed out that these inhomogeneities are connected with composition fluctuations of the type Sr2Fe1+x Mo1-x O6 with Fe-rich (x > 0) and Mo-rich (x < 0) regions. Dedicated to Prof J Gopalakrishnan on his 62nd birthday.  相似文献   
5.
The physical structure and compatibility of solution-cast Antheraea pernyi/Bombyx mori silk fibroin blend films were stuided by differential scanning calorimetry (DSC), thermomechanical (TMA) and thermogravimetric (TGA) analysis, dynamic viscoelastic measurement, infrared spectroscopy, and x-ray diffractometry. The DSC curves of the blend films showed independent endotherms at 280 and 358°C, corresponding to the thermal decomposition of B. mori and A. pernyi silk fibroins with random coil conformation. The intensity was roughly proportionate to the amount of each component in the blend. The thermal behavior corresponding to the conformational transitions induced by heating on A. pernyi and B. mori silk fibroins overlapped in the temperature range 190–230°C. Thermal expansion and contraction properties, as well as weight retention behavior of the blend films were intermediate between the pure components, as shown by the TMA and TGA curves. The onset temperature of the storage modulus curve decreased markedly, approaching that of B. mori silk fibroin film when the amount of this component in the blend increased. The loss modulus curve of the blend films showed two peaks at ca. 190 and 210°C, the former corresponding to B. mori, and the latter to A. pernyi silk fibroin. Infrared spectra of the blends exhibited absorption bands characteristic of the pure components overlapping in the spectral region 2000–400 cm?1. The x-ray diffraction peaks at 23 and 21.5°, attributed to the crystalline spacings of A. pernyi and B. mori fibroins, respectively, overlapped in the diffraction curves of the blends, while the peak at 11.4°, of A. pernyi, increased as the content of this fibroin in the blend increased. The degree of crystallinity, calculated from the x-ray diffraction curves, diminished as the amount of B. mori silk fibroin decreased. A low degree of compatibility exists between the two fibroins when they are cast from aqueous solution in the experimental conditions adopted in this work. © 1994 John Wiley & Sons, Inc.  相似文献   
6.
M. Keane 《Applied Acoustics》2007,68(10):1104-1117
A new method is presented for splitting musical notes into tonal and broadband components by removing the harmonic peaks from the spectra. This method was used to analyse the key vibrations of eight pianos (four grand and four upright). The broadband component of vibrations was found to be more intense in the upright pianos than in the grand pianos, while no such difference was found in the tonal component. As grands are considered to be superior to uprights, this suggests that it may be possible to improve upright pianos by reducing the strength of the broadband component of vibrations.  相似文献   
7.
The crystal structure of a novel ferrocene derivative with potential flame-retardant/smoke-suppressant activity, 1,4,5,6,7,7-hexachloro-2-endo-ferrocenyl-hydroxymethyl-3-endo-hydroxymethyl-5-norbornene, has been determined. Some of the carbon–carbon bonds within the chlorendic residue are unusually long, and there is no interaction between the hydroxyl groups and the iron atom. There is evidence of intramolecular hydrogen bonding between the two hydroxyl groups.  相似文献   
8.
Crystal Structure of Hexamine Cyclotriphosphazene, P3N3(NH2)6 In the presence of KNH2 hexamine cyclotriphosphazene semi ammoniate (molar ratio 12:1) in NH3 gives crystals of solvent free P3N3(NH2)6 within 5 d at 130°C and p(NH3) = 110 bar. The structure was solved by X-rax methods: P3N3(NH2)6: P21/c, Z = 4, a = 10.889(6) Å, b = 5.9531(6) Å, c = 13.744(8) Å, β = 97.83(3)°, Z(Fo) = 1 721 with (Fo)2 ≥ 3σ(Fo)2, Z(var.) = 157, R/Rw = 0,036/0,041 The structure contains columns of molecules P3N3(NH2)6 all in the same orientation. The six-membered rings within one molecule have boat conformation. The columns are stacked together in a way that one is surrounded by four others shifted by half a lattice constant in direction [010]. Strong hydrogen bridge-bonds N? H…?N connect molecules within the columns and between them.  相似文献   
9.
The structure of titanyl dipivalylmethanate TiO(dpm)2 has been studied by X-ray diffraction analysis. The compound has a molecular structure formed by isolated centrosymmetrical dimers [TiO(dpm)2]2; the unit cell contains two structurally related, crystallographically unique binuclear molecules. The Ti...Ti distance in the dimer is 2.73 Å. Crystal data for Ti2C36H76O10: a = 32.477(6) Å, b = 14.409(3) Å, c = 25.630(5) Å; β = 107.82(3)°, space group C2/c, Z = 8, d calc = 1.002 g/cm3.  相似文献   
10.
A non-empirical molecular orbital method, particularly suitable for calculations on cage-like molecules, is described. The method uses as basis functions the set of free-electron functions which are the solutions of Schrödinger's equation for an electron confined between two concentric, spherical potential energy barriers. Application of the theory to the SCF calculation of the energies of the delocalized electrons in benzene and tetrasulphur tetranitride shows that the model is capable of interpreting the properties of such systems. However, it does highlight a difficulty in the calculation of excited state energies with one-centre models which appears to be largely unrecognized.Extension of the method to a consideration of all the valence electrons, using P4 as an example, reveals problems the origin of which is an inadequate treatment of the core electrons. It is suggested that these problems may best be dealt with by use of a suitable pseudo potential.  相似文献   
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