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51.
Field desorption mass spectra of underivatized oligoglycosides of spirostanol and its congeners and of hederagenin revealed the molecular weight and structural information. The basic predominance of the formation of stable ions of highly polar natural products (with 5–17 free OH functions) is clearly demonstrated. After the extraction and purification procedure from plant material the samples contained inorganic salts in concentrations between 0.01 and 0.1%. These salt impurities, mostly alkali halides, strongly promoted the attachment of alkali cations to the intact molecules and their fragments. The ions produced gave analytical information not only for the confirmation of the molecular weight but also for the identity of the aglycone and, to some extent, for the sequence of the sugars in the oligoglycosides. All spectra were recorded on photoplates at a resolution of better than 15000 and enabled the evaluation of the elemental composition of the ions generated. The drawbacks and merits of integrating ion recording using the photoplate for FD investigations of highly polar substances are discussed. 相似文献
52.
Bang JK Naka H Teruya K Aimoto S Konno H Nosaka K Tatsumi T Akaji K 《The Journal of organic chemistry》2005,70(25):10596-10599
[reaction: see text] The solid-phase Horner-Emmons reaction was successfully applied for the convenient syntheses of olefin-containing protease inhibitors. The isomerization during the solid-phase Horner-Emmons reaction can be minimized simply by the use of an appropriate amount of the base. The synthesized olefin peptides, which have an olefin gamma-amino acid at the scissile site, were found to act as effective inhibitors for the HTLV-1 protease for the first time. 相似文献
53.
Umebayashi Y Mroz B Asada M Fujii K Matsumoto K Mune Y Probst M Ishiguro S 《The journal of physical chemistry. A》2005,109(21):4862-4868
Solvation structure of the zinc(II) ion in N,N-dimethylpropionamide (DMPA) was studied by Raman spectroscopy at varying temperature and by quantum mechanical calculations. No significant ion-pair formation was found for the Zn(ClO4)2 solution in the molality range m(Zn) < 1.5 mol kg(-1), and the solvation number of the zinc(II) ion was determined to be 4, indicating that 6-coordination of DMPA is sterically hindered. Interestingly, DMPA molecules are under equilibrium between planar cis and nonplanar staggered conformers, and the latter is more preferred in the coordination sphere, while the reverse is the case in the bulk. The DeltaG degrees , DeltaH degrees , and TDeltaS degrees values of conformational change from planar cis to nonplanar staggered in the coordination sphere were obtained to be -0.9, -8.5, and -7.5 kJ mol(-1), respectively. Density functional theory (DFT) calculations show that the planar cis conformer is more favorable than the nonplanar staggered one in the 1:2 cluster, as is the case for a single DMPA molecule and H(DMPA)+, indicating that there hardly occurs solvent-solvent interaction through the metal ion in the Zn2+-DMPA 1:2 cluster. On the other hand, the SCF energy of [Zn(planar cis-DMPA)4-n(nonplanar staggered DMPA)n]2+ (n = 0-4) decreases with increasing n, implying that the nonplanar staggered conformer is preferred in the solvate ion. It is thus concluded that solvent-solvent interaction through space, or solvation steric effect, plays a crucial role in the conformational equilibrium in the coordination sphere of the four-solvate metal ion. 相似文献
54.
The resistivity of doped semiconductor Si: P in the intermidiate concentration range was measured in low temperature region down to 10 mK. In the lowest temperatures Mott's formula for the variable range hopping is shown to be not applicable and T-n-like temperature dependence of resistivity is confirmed. The Importance of the level correlation in the random system is discussed. 相似文献
55.
Tetraalkylphosphonium-based amino-acid ionic liquids show lower viscosities and higher decomposition temperatures (>300 degrees C) than previously reported ammonium-based amino-acid ionic liquids. 相似文献
56.
Kawasaki T Suzuki K Hatase K Otsuka M Koshima H Soai K 《Chemical communications (Cambridge, England)》2006,(17):1869-1871
Enantiomorphous crystals composed of achiral hippuric acid, i.e., naturally occurring N-benzoylglycine, have been used successfully as chiral inducers in enantioselective synthesis in combination with asymmetric autocatalysis to afford the product with extremely high enantiomeric excess. 相似文献
57.
58.
Shimada T Kondoh H Iwasaki M Nakai I Nagasaka M Amemiya K Orita H Ohta T 《The journal of physical chemistry. B》2006,110(41):20507-20512
The adsorption structure of NO on the reconstructed Pt(110)-(1 x 2) surface was studied with X-ray photoelectron spectroscopy (XPS), X-ray photoelectron diffraction (XPD), low-energy scanned-angle photoelectron diffraction (LESA-PD), and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The experiments were performed at 180 K, where no surface lifting from (1 x 2) to (1 x 1) takes place after NO adsorption. XPS indicates that the (1 x 2) unit cell of the Pt(110) surface contains 1.5 NO molecules at the saturated coverage. XPD and LESA-PD analyses allow us to propose a structural model for the NO adlayer, where two-thirds of the NO molecules in the (1 x 2) unit cell are adsorbed on the atop site of the close-packed Pt rows (ridges) along the [10] direction with an inclined geometry and one-third of the NO molecules adsorb on the bridge site between the Pt ridges with an upright configuration. This model is supported by the N K-edge NEXAFS experiments and is consistent with the recently reported model based on the density functional theory (Orita, H.; Nakamura, I.; Fujitani, T. J. Phys. Chem. B 2005, 109, 10312). 相似文献
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