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31.
Bérangère C Caussarieu N Morin P Morin-Allory L Lafosse M 《Journal of separation science》2004,27(12):964-970
An original system which uses Porous Graphitic Carbon as support and a mixture of organic solvents as mobile phase is proposed for the analysis of triterpenic acids by liquid chromatography. The separation of betulinic acid, ursolic acid, oleanolic acid, and 18alpha- and 18beta-glycyrrhetinic acids was carried out within a short time and monitored by evaporative light scattering detection as universal detection method. Molecular modelling studies show that the main contribution to the selectivity comes from the electrostatic interaction characterised by the dipole moment of the products. 相似文献
32.
The voltammogram of aryldiazonium tetrafluoroborates in acetonitrile (ACN), at low concentration, shows a first one-electron wave followed at a more negative potential by a small second wave; this last one corresponds to the reduction of the radical formed at the level of the first wave. Simulation of the voltammogram permits one to determine the standard redox potential of the radical/anion couple Eo(Ph./Ph-) = 0.05 V/SCE and the reduction mechanism of the diazonium cation. An electron transfer concerted with the cleavage of the C-N bond furnishes the aryl radical; this radical undergoes two competitive reactions: reduction at the electrode and H-atom transfer. 相似文献
33.
Claude Moncuit 《Theoretical chemistry accounts》1975,39(3):255-276
The oscillator strengths of the “d-d” transitions of the ion [PtCl4]2? were calculated. The method, based on the evaluation of the MO of the distorted ion, gives results in good accordance with the experimental data. The transition to 1 B 1g (a 1g →b 1g * ), as a consequence of the participation of the orbital 6s, mixed with \(5d_{z^2 } \) in \(a_{1_g } ,a_{1_g } \) is characterized by a very low intensity in the case of thex,y polarization. 相似文献
34.
35.
Bossée A Afonso C Fournier F Tasseau O Pepe C Bellier B Tabet JC 《Journal of mass spectrometry : JMS》2004,39(8):903-912
Peptide metallation with Cu2+ was explored in the negative ESI mode using an ion trap mass spectrometer. Under these conditions, the [(M-3H) + CuII]- species formed were investigated under low-energy collision-induced dissociation conditions. MS2 experiments indicate a very different behavior of CuII metallated complexes compared with [M-H]- species. CuII induces an easy loss of CO2 and specific side-chain cleavages (by radical losses) at the C-terminal residue, as observed previously by prompt 'in source' dissociation experiments. The loss of CO2 yields an unstable carbylide that leads to further dissociations involving the migration of a proton or a hydrogen radical (through the reduction of CuII). Multistage MS3 experiments were carried out to rationalize this behavior. Fragmentation pathways are proposed in order to explain the product ions observed. The side-chain radical loss at the C-terminus was demonstrated to be a consecutive process. Finally, evidence is provided that the specific side-chain cleavages can be used for the differentiation of Leu/Ile and Gln/Lys residues when they are located at the C-terminus. The existence of a zwitterionic form in the case of the anionic YGGFK-CuII complex is proposed. 相似文献
36.
The I-E response of the liquid membrane of the calcium selective electrode is studied under constant or linearly varying current and voltage. An increase in the membrane resistance, recorded when an electrical current crosses the membrane, is due to the outflow of Cl? ions initially present in the membrane. When calcium ions are replaced by alkaline ions inside the membrane at constant current, the decrease of the membrane resistance due to an ion exchange is in agreement with the conductivity measurements (Part II). When the applied voltage is imposed besides the ion exchange one must take into account the interfacial overpotential to explain the important rectification effect observed. The interfacial transfer constant rate of alkaline ions seems greater than that of Ca2+ ion. 相似文献
37.
A surface counterion titration method was used to monitor the interaction of monovalents cations (Li(+), Na(+), TMA(+)) with the surface of alumina-coated TiO(2) particles in concentrated media at different pH and electrolyte concentrations. This method allows measuring separately the negative and positive contribution to the surface charge. It showed that Cl(-) and TMA(+) are indifferent ions, but Li(+) and Na(+) specifically adsorb on the non-ionized alumina surface sites. The binding sequence of cations is Li(+)>Na(+)>TMA(+) at all ionic strengths investigated and is consistent with the structure-making and structure-breaking model developed a few decades ago. Polyacrylic acid (PAA) previously neutralized with the corresponding hydroxide (LiOH, NaOH, TMAOH) has been adsorbed on the alumina surface at different pH. The polymer counterion has a significant influence on the polymer adsorption. The sequence of the surface coverage as a function of the polymer counterion follows the order Li-PAA > Na-PAA > TMA-PAA. The much higher surface coverage with Li-PAA and Na-PAA compared to TMA-PAA is explained by the specific adsorption of Li-PAA and Na-PAA on the nonionized alumina surface sites, the same way LiCl and NaCl do. 相似文献
38.
Novel large polyazadioxime molecules 4,5,8,9-tetraaza-3,6,7,10-tetramethyl -3,5,7,9-dodecatetraene-2, 11-dione-2, 11-dioxime (H2doxN4) and 4,5,8,9,12, 13-hexaaza-3,6,7,10,11,14-hexamethyl-3, 5,7,9,11,13-hexadecahexane-2,15-dione-2, 15-dioxime (H2doxN6) were synthesized. The molecular geometries of these molecules as well as smaller dioxime molecules, H2dox and H2doxN2 were optimized by using modified intermediate neglect of differential overlap (MNDO) calculations. The optimized conformations for all the molecules under study are close to the all-E, all-s trans conformation of C2h symmetry group. However, the energy barriers of internal rotation around the N-N single bonds were found to be low. Therefore some distortions of the polyazabackbone through internal rotation the N-N bonds have been evidenced. By infrared and Raman spectroscopies in the solid state as well as in solution. From the MNDO calculations and vibrational spectroscopy, the polyaza chain molecules under study appear as a poorly conjugated system and can be represented as a sequence of single and double bond alternation. 相似文献
39.
Claude Lavalle Alain Leborgne Nicolas Spassky Robert E. Prud'homme 《Journal of polymer science. Part A, Polymer chemistry》1987,25(5):1315-1328
β-(trichloromethyl)-β-propiolactone (CCl3-PL), β-(trifluoromethyl,methyl)-β-propiolactone (CF3, Me-PL) and β-(trifluoromethyl,ethyl)-β-propiolactone (CF3,Et-PL) have been obtained by the reaction of ketene with chloral, 1,1,1-trifluoroacetone and 1,1,1-trifluorobutanone, respectively. Chiral catalysis lead to optically active monomers. The enantiomeric excess of the lactones has been measured by 1H-NMR spectroscopy, in the presence of 2,2,2-trifluoro-1-(9-anthryl)ethanol or an europium chiral shift reagent. Polymerizations have been carried out in bulk or in toluene, at 60°C or 80°C, using mainly organometallic initiators. The Polymers become insoluble and crystalline at enantiomeric excesses over 80% for CCl3-PL and 70% for CF3,Me-PL. Melting temperatures were recorded from 238 to 268°C for poly(CCl3-PL) and from 78 to 100°C for poly(CF3,Me-PL), depending upon the molecular weight and the enantiomeric excess. The 13C-NMR specroscopy of poly(CCL3-PL) indicates that the polymerization of the corresponding lactone leads to polymers of increasing degrees of isotacticity with the enantiomeric excess of the monomer. 相似文献
40.
Edwige Jeanneau-Nicolle Claude Bosso Martine Benoit-Guyod Grard Leclerc 《Journal of mass spectrometry : JMS》1993,28(1):37-41
The electron impact mass spectra of two series of 5-oxo-tetrahydro-5H-thiazolo [3,2-a]pyrimidine-6-ethylcarboxylates and 7-oxo-tetrahydro-7H-thiazolo [3,2-a]pyrimidine-6-ethylcarboxylates were measured and fragmentation patterns examined. Structures were assigned from analysis of oxo molecular ion fragmentations. Compounds of the 5-oxo series gave an [M – CO2C2H5]+ fragmentation whereas compounds of the 7-oxo series gave three characteristic cleavages. This decomposition was confirmed for one pair of isomers by high-resolution mass spectrometry and unimolecular mass-analysed ion kinetic energy spectrometry. Electron impact mass spectrometry is a convenient method for assigning structures of 5- and 7-oxo regioisomers of tetrahydrothiazolo[3,2-a]pyrimidine-6-carboxylates. 相似文献