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991.
Torres-Lapasió JR García-Alvarez-Coque MC Bosch E Rosés M 《Journal of chromatography. A》2005,1089(1-2):170-186
The problems associated to the modelling and optimisation of the chromatographic resolution of mixtures involving ionisable solutes at varying pH and acetonitrile content are discussed. Several retention models that separate the contributions of solute, column and stationary phase, were used. The retention was predicted with low errors in large pH domains (2-12), which was an essential requirement to face the optimisation of resolution. The selected mixture was particularly problematic under the viewpoint of resolution, owing to the excessively diverse acid-base behaviour of solutes. This variety led to sudden drops in retention at different pH for each solute, yielding numerous peak crossing, which made finding shared regions of high resolution especially difficult. Conventional resolution diagrams for these situations are scarcely informative, since both the overall and the worst elementary resolutions drop to zero if at least two compounds remain overlapped, even when all the others are baseline resolved. A new chromatographic objective function is proposed to address this drawback. This function, called "limiting peak count", is based on the limiting peak purity concept, and measures the success in the resolution focusing on the resolved solutes, in contrast to conventional resolution assessments that attend mainly to the least resolved solutes. Limiting peak count yields the same result as conventional assessments when full resolution is possible, but it is also able to discriminate the maximal resolving power in low-resolution situations. It offers a different perspective to that given by the complementary mobile phases approach, and the computation is far simpler. 相似文献
992.
A thermodynamic analysis of the interaction between fourteen different molar mass poly(ethylene oxide)s (PEO) and sodium dodecyl sulfate (SDS) based on the measured surfactant-binding isotherms is given. The surfactant-binding isotherms were determined by the potentiometric method in the presence of 0.1 M inert electrolyte (NaBr). It was found that there is no PEO/SDS complex formation if M(PEO) < 1000. In the molecular weight range 1000 < M(PEO) < 8000, the critical aggregation concentration (cac) and the surfactant aggregation number are decreasing as the polymer molecular weight increases. The saturated bound surfactant amount is proportional to the number concentration of the polymer in this molecular weight range. If M(PEO) exceeds approximately 8000, the cac does not depend on the polymer molar mass, and the saturated bound amount of the surfactant becomes proportional to the mass concentration of the polymer. It was also observed that independently of the polymer molecular weight the surfactant aggregation number increases as the equilibrium surfactant monomer concentration increases from the cac to the critical micellar concentration (cmc). Finally, it was demonstrated that only one polymer molecule is involved in the complex formation independently of the polymer molecular weight. 相似文献
993.
994.
Cortés-Jácome MA Toledo JA Angeles-Chavez C Aguilar M Wang JA 《The journal of physical chemistry. B》2005,109(48):22730-22739
WO3-ZrO2 catalysts were synthesized by precipitating the aqueous solutions of zirconium oxynitrate and ammonium metatungstate with ammonium hydroxide. The white slurry precipitate was treated under three different conditions. In the as-made materials, the amorphous phase was formed in the aged and refluxed samples, while well-crystallized tetragonal and monoclinic phases were obtained in the hydrothermally treated sample. The real amount of tungsten loaded in the samples was similar for the three samples, independently of the treatments; however, the tungsten surface atomic density in the annealed WO3-ZrO2 samples varied between 6 and 9 W atoms/nm2. Two different contrast types of aggregates were determined by scanning electron microscopy, the white particles which are rich in W, and the gray ones which are rich in zirconium; both of them were formed in the calcined solids prepared under aging or reflux condition. A very high dispersion of tungsten species on the zirconia surface was achieved in the hydrothermally treated sample. The degree of the interaction between WO(x) and ZrO2 surface strongly modified the Zr-O bond lengths and bond angles in the structure of tetragonal zirconia as proved by X-ray diffraction analysis and the Rietveld refinement. The catalyst obtained under hydrothermal condition exhibited the highest dispersion of tungsten species in the zirconia, which in turn causes strong structural deformation of the tetragonal ZrO2 phase responsible of the strongest surface acidity and, consequently, the optimum catalytic activity for n-hexane isomerization. 相似文献
995.
Ortica F Moustrou C Berthet J Favaro G Samat A Guglielmetti R Vermeersch G Mazzucato U 《Photochemistry and photobiology》2003,78(6):558-566
A photophysical and photochemical study of a biphotochromic compound where two naphthopyran units are linked by an acetylene-thiophene-acetylene bridge has been carried out in toluene. Both fluorescence and intersystem crossing to the triplet manifold were found to compete with the photocoloration process. Two photoproducts (transoid-trans and transoid-cis stereoisomers), absorbing at approximately 480 nm and corresponding to the opening of a single photochromic unit, were detected by spectrophotometric analysis after short irradiation time in diluted solution and identified by 1H-nuclear magnetic resonance (NMR) spectroscopy. After prolonged irradiation at 228 K of highly concentrated solutions (up to 3 x 10(-3) mol dm(-3)), two additional isomers, absorbing at approximately 550 nm, were formed. Their NMR spectra indicate the opening of both photochromic units. An interesting effect of selective vibronic excitation was found, showing that the photoreaction is favored at excited vibronic levels to the detriment of the radiative relaxation. 相似文献
996.
A New Gamma-Ray Spectrum Catalog for PGAA 总被引:1,自引:0,他引:1
Zs. Révay G. L. Molnár T. Belgya Zs. Kasztovszky R. B. Firestone 《Journal of Radioanalytical and Nuclear Chemistry》2000,244(2):383-389
A major obstacle to the use of the prompt gamma activation analysis (PGAA) method has so far been the lack of a suitable library. Therefore, new measurements have been performed at the PGAA facility at Budapest Research Reactor (BRR) in order to create a prompt -ray catalog for qualitative and quantitative analysis. Prompt -ray energies and associated k
0-factors have been determined by internal standardization. The resulting catalog contains prompt -ray data from neutron capture and other reactions such as (n,), and decay -ray data from short-lived reaction products. Data have been measured for nearly all stable elements, from hydrogen to uranium. Generally, data for several isotopes are given, to enable isotopic analysis as well. 相似文献
997.
Special aspects of ion-selective electrodes relevant to applications in flow-through systems are discussed. The predominant role of the dynamic response characteristics of the sensor, especially in flow-injection analysis, is emphasized. Indirectly, these characteristics can affect the linear response range, the detection limit and the selectivity properties of the sensors. As examples, flow-injection methods are described for the determination of fluoride in rain-water samples and of potassium ion activity in blood sera. 相似文献
998.
J. Réffy 《Journal of organometallic chemistry》1975,97(2):151-157
CNDO/2 calculations for a series of MexH3?xSi (where x = 0,1,2,3) free radicals confirm the suggestion, based on electron spin resonance measurements and chemical evidence, that these radicals are not planar. The deviation from planarity decreases with increasing number of methyl groups, but the angle between the carbonsilicon bond and the plane of an assumed planar configuration is the same for methylsilyl, dimethylsilyl, and trimethylsilyl radicals. 相似文献
999.
The crystalline chiral auxiliaries , and were prepared from camphor-10-sulfonyl chlorides in 2 steps. Their readily accessible acrylates underwent efficient asymmetric diels-alder additions to cyclopentadiene, the topicity of which agrees with X-ray evidence. 相似文献
1000.