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71.
Tran H Joubert P Bonamy L Lavorel B Renard V Chaussard F Faucher O Sinardet B 《The Journal of chemical physics》2005,122(19):194317
With the aim of temperature diagnostic, femtosecond time-resolved CARS (coherent anti-Stokes Raman spectroscopy) is applied to probe H2 in H2-N2 mixtures. In a first part, a Lorentzian profile is used to model the femtosecond CARS response. A difference between the experimental broadening and the expected one is observed in the collision regime. The observed broadening increases strongly in an inhomogeneous way with respect to the perturber concentration. This is of considerable importance for temperature measurements. In a second part, we show that in the collision regime, this inhomogeneous broadening is due to the speed dependence of the collisional parameters and the memory effects of the radiator speed. A new modelization of the time-resolved CARS response taking into account the speed memory effects is presented and applied to the temperature diagnostic in H2-N2 mixtures. The numerical results are in good agreement with experiments. 相似文献
72.
Ahn YH Park EJ Cho K Kim JY Ha SH Ryu SH Yoo JS 《Rapid communications in mass spectrometry : RCM》2004,18(20):2495-2501
The enrichment of phosphopeptides using immobilized metal ion affinity chromatography (IMAC) and subsequent mass spectrometric analysis is a powerful protocol for detecting phosphopeptides and analyzing their phosphorylation state. However, nonspecific binding peptides, such as acidic, nonphosphorylated peptides, often coelute and make analyses of mass spectra difficult. This study used a partial chemical tagging reaction of a phosphopeptide mixture, enriched by IMAC and contaminated with nonspecific binding peptides, following a modified beta-elimination/Michael addition method, and dynamic mass analysis of the resulting peptide pool. Mercaptoethanol was used as a chemical tag and nitrilotriacetic acid (NTA) immobilized on Sepharose beads was used for IMAC enrichment. The time-dependent dynamic mass analysis of the partially tagged reaction mixture detected intact phosphopeptides and their mercaptoethanol-tagged derivatives simultaneously by their mass difference (-20 Da for each phosphorylation site). The number of new peaks appearing with the mass shift gave the number of multiply phosphorylated sites in a phosphopeptide. Therefore, this partial chemical tagging/dynamic mass analysis method can be a powerful tool for rapid and efficient phosphopeptide identification and analysis of the phosphorylation state concurrently using only MS analysis data. 相似文献
73.
Bhatia SK Tran K Nguyen TX Nicholson D 《Langmuir : the ACS journal of surfaces and colloids》2004,20(22):9612-9620
We present new simulation results for the packing of single-center and three-center models of carbon dioxide at high pressure in carbon slit pores. The former shows a series of packing transitions that are well described by our density functional theory model developed earlier. In contrast, these transitions are absent for the three-center model. Analysis of the simulation results shows that alternations of flat-lying molecules and rotated molecules can occur as the pore width is increased. The presence or absence of quadrupoles has negligible effect on these high-density structures. 相似文献
74.
75.
Single crystal structure determinations prove the two pyridine substituents in di(2-pyridyl)ketone (H4C4NC)2C=O to be twisted out of the carbonyl skeleton plane by torsion angles (OCCN) of 41° and –163°, in contrast to their planar arrangement in azo-di(2-pyridine) H4C4NC)-N=N-(CNC4H4). In order to rationalize the surprising difference between the two isoelectronic molecules, approximate PM3 enthalpy of formation hypersurfaces have been calculated for each of the two ring torsions, which are assumed to be the dominant ones among the 3N – 6 = 60 degrees of freedom. For both the ketone and the azo derivative, global minima are calculated, the torsion angles of which deviate from the crystal structure results, and, therefore, support the assumption that both the experimentally determined twisting of di(2-pyridyl)ketone as well as the flattening of azo-di(2-pyridine) might be affected by the crystal packing. 相似文献
76.
Synthesis and spectral characterization of some complexes of platinum(II) containing η-methyleugenol
Several complexes of the formula trans-[Pt(Meug)(Am)Cl2], Meug: methyleugenol (4-allyl-1,2-dimethoxybenzene), a η2-coordinated olefin, and Am: ammine, methylamine, diethylamine, o-toluidine, m-toluidine, p-toluidine, o-anisidine, m-anisidine and p-anisidine have been prepared. UV, IR, Raman, 1H NMR, 13C NMR and 2D NMR spectra of the complexes were recorded and analyzed. 相似文献
77.
AbstractA simple, efficient, and metal-free methodology for the preparation of 2-mercaptobenzothiazole and derivatives in excellent yields via microwave-assisted pathway is reported. Our condition provides a convenient protocol for the synthesis of a diverse collection of 2-mercaptobenzothiazoles and 6-(4-substituted-1H-1,2,3-triazol-1-yl)-2-mercaptobenzothiazoles with a very simple purification process. This report provides an alternative protocol for fast access to the wide range of compounds for sequence synthesis and biological studies. 相似文献
78.
A. Serier J. P. Pascault Thanh My Lam 《Journal of polymer science. Part A, Polymer chemistry》1991,29(8):1125-1131
The hydrolysis and reactions of alkoxy silane groups have been studied on a model compound (TA) prepared from 2 mol of phenyl glycidyl ether and 1 mol of aminopropyl triethoxy silane. At low (40°C) and high (140°C) temperatures, the monomer conversion and the evolution of the molecular mass are followed by size exclusion chromatography (SEC). During the same reaction time, the evolution of the functional groups, hydroxyl CH? OH, ethoxy ? O? C2H5, and siloxane Si? O? Si, is observed by FTIR spectroscopy. Without the presence of water, reactions between hydroxyl and ethoxy silane lead to gelation at the end of the reaction. A by-product, probably a cyclic tetramer is also formed. After the hydrolysis, the reaction of the model compound is quite different. The product of reaction is always soluble, even after a treatment at high temperatures, and the evolution of the molecular mass versus the reaction time seems to correspond to the condensation giving a dead cyclic tetramer. From this study it is evident that the curing cycle has a great influence on the properties of the interface of a composite based on a epoxy matrix. 相似文献
79.
Tae -Kyu Ha 《Theoretical chemistry accounts》1977,43(4):337-349
Configuration interaction (CI) studies of ground, n *, * * electronically excited states are reported for pyridine N-oxide. The transition energy to the lowest * excited 1
B
2 state is calculated at 4.35 eV, compared to the experimental spectrum range of 3.67–4.0 eV. This state lies below the lowest n * excited 1
A
2 state calculated at 4.81 eV above the ground state. The only experimentally reported triplet state at 2.92 eV above the ground state is predicted to be the 3
A
1 (*) state. The calculated energy lies at 3.27 eV. Numerous other high-lying singlet states as well as the triplet states have also been calculated. The intramolecular charge transfer character of the ground and the excited states have been studied in terms of the calculated dipole moment and other physical properties. 相似文献
80.
[reaction: see text] Three novel domino reaction processes have been discovered and developed that employ the regioselective and stereoselective [Rh(CO)(2)Cl](2)-catalyzed alkylations of allylic trifluoroacetates with alpha-substituted sodiomalonates followed by an intramolecular Pauson-Khand annulation, a [5 + 2] cycloaddition, or a cycloisomerization. A unique aspect of the methodology is that a single catalyst is used to effect sequential transformations simply by increasing the temperature for the second reaction. 相似文献