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951.
M. Hanson 《Chromatographia》1994,39(7-8):431-437
Summary Pressure/temperature variation in SFC was shown to influence selectivity towards steroids. Major changes were observed for polar column packings compared to non-polar packings and variation of the amount of modifier showed that this is valid over the whole investigated range. The effect is underlined by a fall in resolution in the low density range (low pressure/high temperature) for polar stationary phases and appears to be significantly larger than for non-polar phases. Major selectivity shifts induced by variation of the physical properties of the mobile phase are considered to be due to the greater effect of polar modifiers on the nature of polar stationary phases than on non-polar phases. 相似文献
952.
Summary Experiments and simulations prove that correlation chromatography can greatly reduce the disadvantage of a non-linear response of the chromatographic column. A factor that has been accepted as being an important source of error in correlation or multiplex chromatography, has been shown not to be. Separations affected, improve dramatically when correlation chromatography is used, and a substantial amount of correlation noise only arises when there is a large difference in separation between a conventional chromatogram and a correlogram.A model has been developed for simulating these nonlinearities. It is shown that, especially for correlation chromatography, the simulation results match the practical measurements very well. 相似文献
953.
954.
Separation of 23 dansylated amino acids by micellar electrokinetic chromatography at low temperature
Summary The baseline separation of 23 dansylated amino acids (including 3 didansylated species) is reported. Lowering of the analysis
temperature and fine control of the surfactant concentration were essential in obtaining this result. Calibration graphs with
good linearity were obtained. 相似文献
955.
The coordination chemistry of beryllium with particular emphasis on chelates under physiological or near physiological conditions is surveyed. Hard donors such as oxygen are emphasized; equilibrium data and formation constants are reported as an indication of the strength of the complex. 相似文献
956.
J. Escudi C. Couret H. Ranaivonjatovo J. Satge 《Coordination chemistry reviews》1994,130(1-2):427-480
During the last 10 years, several compounds of the type Ge=X (X = C, Ge, N, P, S) have been isolated as monomers. The stabilization of such derivatives, which are generally highly polymerizable, was achieved by using very bulky groups both on the germanium atom and on the heteroelement X. Conjugation (particularly in a few germenes and germaimines) and intramolecular or intermolecular coordination with oxygen or nitrogen, also contributes, in some cases, to the stabilization. The X-ray analyses of such compounds show a significant bond shortening of the double bond (8–10%) relative to the corresponding single bond and a planar or nearly planar germanium. These doubly bonded germanium derivatives are usually thermally stable but must be handled in an inert atmosphere because of their high sensitivity to oxygen and moisture; they are extremely reactive, much more than the corresponding carbon analogues. Nearly quantitative additions on the double bond have been observed with electrophiles and nucleophiles, and various types of cycloadditions also occur. Except in one case, a germylene behavior has not been observed, proving that such compounds retain their structural integrity in solution. 相似文献
957.
The copolymerization of methyl methacrylate and methacrylic acid in isopropyl alcohol is studied by kinetic, dynamic laser scattering and 13C-NMR methods. Correlations are established between the dependence of the copolymerization rate, the apparent average molecular weight, the diffusion coefficients and the configurational triad composition on the monomer feed. These correlations and the fact that both copolymerization constants are smaller than unity (rMMA = 0.63 ± 0.03; rMA = 0.25 ± 0.05) are in good agreement with the assumption that a comonomer complex takes part in the propagation reaction. A new Markov chain method for the estimation of the configurational triad mole fraction which accounts for the complex participation in a macromolecule formation is developed. Qualitative criteria for evidence the participation of the comonomer complex in copolymerization are proposed using experimental and terminal model calculated mole fractions of the compositional triads and diads. 相似文献
958.
Twelve series of linear oligomers of four different degrees of polymerization (xn = 8.77−41.55), having a common perfluorinated random copolymeric chain as molecular body and two equal foreign end units of one of the types listed in Table 1, have been synthesized by derivatization of base samples of one of them having a diolic---CH2OH functionality. The glass transition temperature Tg of all the series was measured and thus examined as a function of xn. A clear end unit effect is observed, dominantly determined in every series by chemical nature and structure of the end units, quantitatively expressed at any xn by different positive or negative Tg deviations from the common asymptotic Tg∞ value. The results are also discussed in terms of copolymer end effect and of relation between Tg and end copolymeric composition. 相似文献
959.
New tricyclic spacers, readily available through fourfold Mannich reaction of substituted dibenzyl ketones, were introduced into a series of ten H2O-soluble cyclophanes with spacious preorganized cavity binding sites. These spacers provide H2O-solubility with amine or crown-ether functionality remote from the cyclophane cavity while directing functional groups such as keto or OH groups in a precise geometrical array inside the cavity. The cyclophanes were designed to include organic substrates via a combination of apolar and specific polar functional group interactions. The X-ray crystal-structure analysis of the tritopic receptor 18 with one potential neutral-molecule and two cation-binding sites showed a large rectangular open cavity with dimensions of roughly 9 × 14 Å and a spacing of 9.7 Å between the O-atoms of two convergent C?O groups. Despite the binding-site preorganization, cyclophanes incorporating two of the new spacers did not show any substrate binding in aqueous solutions. The failure of these systems to function as receptors is mainly due to steric hindrance to important cyclophane aromatic ring-guest interactions. Also, the favorable solvation of the intracavity functionality may prevent the formation of complexes. Hybrid receptors constructed from the novel spacers and diphenylmethane units were found to bind flat aromatic substrates as well as bulky [4.2]paracyclophanes. The observed large differences in stability (ΔΔG°> 2 kcal mol?1) of the complexes formed by three structurally closely related hybrid receptors with convergent C?O, OH or CH2 groups and 6-hydroxynaphthalene-2-carbonitrile as guest can be explained by a strong solvation effect of the convergent functional groups on apolar inclusion complexation. 相似文献
960.
Helmut Schmidhammer Eva Scherb-Bukowiecki Thomas A. Mayer Peter Schnholzer 《Helvetica chimica acta》1994,77(6):1590-1594
The synthesis of benzazepine analogues of the opium alkaloid noscapine ( 1 ) is described. The benzazepines 2 and 3 were prepared starting from nornarceine ethyl ester ( 4 ; readily available from 1 ) in several steps. X-Ray analysis of compound 2 revealed that it is not a diastereosisomer mixture but a racemate of the threo-form and thus has the same configuration as 1 . 相似文献