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261.
A new mesh refinement technique for unstructured grids is discussed. The new technique presents the important advantage of maintaining the original grid skewness, thanks to the capability of handling hanging nodes. The paper also presents an interpretation of MacCormack's method in an unstructured grid context. Results for a transonic convergent–divergent nozzle, for a convergent nozzle with a supersonic entrance and for transonic flow over a NACA 0012 airfoil are presented and discussed. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
262.
We prove that the orbits of a polar action of a compact Lie group on a compact rank one symmetric space are tautly embedded with respect to Z
2-coefficients.The second author was supported in part by FAPESP and CNPq. 相似文献
263.
Leonardo Chiatti 《Foundations of Physics》1995,25(3):481-490
The concept of transaction, introduced by Cramer in his realistic nonlocal interpretation of quantum mechanics (QM), is herein reformulated in the language of the Feynman graphs' technique. 相似文献
264.
Atmospheric pressure chemical ionization mass (APCI-MS) and tandem mass spectrometry (APCI-MS/MS) is used to probe the mechanism of the Petasis olefination reaction. Oxatitanacycle intermediates 4 were transferred from solution to the gas phase, detected as 4H+ by APCI-MS with characteristic Ti-isotopic patterns, and structurally characterized by APCI-MS/MS. Detection of 4H+, which upon collision activation dissociates to both 3H+ and Cp(2)TiOH+, fully supports the Hughes mechanism as depicted above. [reaction: see text] 相似文献
265.
266.
Pena AM Boulesteix T Dartigalongue T Schanne-Klein MC 《Journal of the American Chemical Society》2005,127(29):10314-10322
We performed polarization-resolved surface second harmonic generation (SHG) experiments on thin films of collagen I and IV molecules, as well as conventional CD measurements. We found that collagen IV presents little CD and no SHG optical activity, whereas collagen I exhibits large chiroptical effects involving both one-electron and excitonic coupling mechanisms. We estimated that these chiral components enhance the SHG signal from fibrillar collagen in biological tissues by typically a factor of 2. By comparing the distinct behaviors of collagens I and IV in SHG microscopy and in surface SHG experiments, we concluded that SHG microscopy is a sensitive probe of the micrometer-scale structural organization of collagen in biological tissues. 相似文献
267.
Xu X Mei H Wang S Zhou Q Wang G Broske L Pena A Korfmacher WA 《Rapid communications in mass spectrometry : RCM》2005,19(18):2643-2650
Hydroxyproyl-beta-cyclodextran (HPBCD), methyl cellulose (MC), Tween 80 and PEG400 are commonly used in dosing formulations in pharmacokinetic (PK) studies during the early drug discovery stage. A series of studies was designed to evaluate the potential matrix effects of these dosing vehicles when the samples are assayed by high-performance liquid chromatography combined with tandem mass spectrometry (HPLC/MS/MS). These dosing vehicles were dosed into the rats via either an intravenous (IV) or an oral route (PO) and plasma samples were collected for a 24-h post-dose period. Five test compounds with CLog P values ranging from 0.9 to 5.4 were spiked into the collected rat plasma. After protein precipitation, these samples were analyzed using a generic fast-gradient HPLC/MS/MS method. Three popular mass spectrometers (Thermo-Finnigan Quantum with ESI and APCI, AB-Sciex API 3000 with ESI and APCI, and Waters-Micromass Quattro Ultima with ESI) were used to test these plasma samples. Results indicated that there was no observed matrix effect for all five compounds when 20% HPBCD or 0.4% MC was used as the vehicle in either the IV or the PO route, respectively. In addition, 0.1% Tween 80 dosed either IV or PO caused significant ion suppression (50-80%, compared to results obtained from plasma samples free from vehicles) for compounds that eluted at the beginning of the chromatogram. Also, PEG400 when used in an oral formulation caused significant ion suppression (30-50%) for early eluting compounds. These matrix effects were not only ionization mode (ESI or APCI) dependent, but also source design (Thermo-Finnigan, AB-Sciex or Waters-Micromass) dependent. Overall, the APCI mode proved to be less vulnerable to matrix effects than the ESI mode. Some possible mechanisms of these matrix effects are proposed and simple strategies to avoid these matrix effects are discussed. 相似文献
268.
Leonardo Bonsignore Anna Maria Fadda Giuseppe Loy Antonio Maccioni Gianni Podda 《Journal of heterocyclic chemistry》1983,20(3):703-707
The cleavage reaction of some 1,3-benzodioxole derivatives with magnesium bromide and acetic anhydride has been studied. The reactions have been carried out in acetonitrile solution at room temperature. In all of the 1,3-benzodioxoles studied, the opening of the heterocyclic ring with formation of bromides, alkenes and their corresponding products of hydrolysis have been observed. The competitive electrophilic substitution on the benzene ring was very limited and was insignificant when a large excess of the cleavage reagent was used. The structures of newly prepared compounds have been determined by elemental analysis, spectroscopic data and comparison with authentic samples. 相似文献
269.
We report the synthesis, characterization, and spectroscopic properties of a family of trinuclear cyano-bridged mixed-valent compounds, trans-[Ru(II)L(4)[NCFe(III)(CN)(5)](2)](4-), trans-[Ru(II)L(4)[CNFe(III)(CN)(5)](2)](4-), and cis-[Ru(II)(bpy)(2)[NCFe(III)(CN)(5)](2)](4-) (L = pyridine, 4-tert-butylpyridine, and 4-methoxypyridine). Tetraphenylphosphonium salts of complexes trans-[Ru(II)L(4)[NCFe(III)(CN)(5)](2)](4-) (L = pyridine and 4-tert-butylpyridine) crystallize in the space groups C2 and P2(1)/c, respectively, and show a linear arrangement of the metal units and an almost completely eclipsed configuration of the equatorial ligands. An intense band (epsilon approximately 2000-9000 M(-1) cm(-1)) is observed for all of the compounds in the NIR region of the spectrum, not present in the separated building blocks, and strongly solvent dependent. We assign it as a metal-to-metal charge transfer (MMCT) from the Ru(II) to the terminal Fe(III) moieties in the context of a simplified three-center model. The electrochemistry measurements reveal a splitting of the redox waves for the reduction of the iron centers for some of the complexes with a trans configuration between the metal units, ranging from 100 to 260 mV, depending on the substituting pyridine ligand and the solvent, suggesting long-range metal-metal interactions. These interactions are rationalized in terms of the energy matching between the pi-symmetry orbitals of the metals and the cyanide bridge. The one- and two-electron reduced species derived from compounds trans-[Ru(II)L(4)[NCFe(III)(CN)(5)](2)](4-,5-,6-) were characterized in methanolic solution. The mixed-valent Fe(II)-Ru(II)-Fe(III) system exhibits an intense red shifted band in the NIR region of the spectrum, arising from the superposition of MMCT bands from the central Ru(II) to the terminal Fe(III) fragments and from the 1 nm distant Fe(II) to Fe(III) centers. 相似文献
270.
Ribet JP Pena R Maurel JL Belin C Tillard M Vacher B Bonnaud B Colpaert F 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,62(1-3):353-363
{[1-(3-Chloro-4-fluorobenzoyl)-4-fluoropiperidin-4yl]methyl}[(5-methylpyridin-2-yl)methyl]amine, fumaric acid salt (C(20)H(22)ClF(2)N(3)O, C(4)H(4)O(4)) (1) was synthesized and characterized by the complete (1)H, (13)C and (19)F NMR analyses. The conformation of the piperidin ring, in the solution state, was particularly studied from the coupling constants determined by recording a double-quantum filtered COSY experiment in phase-sensitive mode. (1)H NMR line-shape analysis was used, at temperatures varying between -5 and +60 degrees C, to determine the enthalpy of activation of the rotational barrier around the CN bond. Compound 1 crystallizes in the triclinic space group P1 with a=8.517(3) Angstrom, b=12.384(2) Angstrom, c=12.472(3) Angstrom, alpha=70.88(2) degrees, beta=82.04(2) degrees, gamma=83.58(2) degrees. The results strongly indicate that the solid and solution conformations are similar. Thermal stability and phases transitions were investigated by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). Furthermore polymorphism screening was studied from recrystallization of 1 performed in seven solvents and by slurry conversion in water. The X-ray powder diffraction (XRPD) and differential scanning calorimetry results suggested that 1 crystallizes into one crystalline form which melts at 157 degrees C (DeltaH=132 J g(-1)). 相似文献