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281.
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
282.
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
283.
Synthesis of optically active sesquiterpenes with a eudesmane C-skeleton from the chiral starting material thujone involves transformation of a tricyclic intermediate (1R,2R,4S)-1,7-dimethyl-4-(1-methylethyl)tricyclo[4.4.0.02,4]dec-6-en-8-one ( 2 ) into the bicyclic compound β -cyperone ( 5 ). Hydroxylation of 2 at C(5) or C(11) permits subsequent opening of the cyclopropane ring and rearrangement to β -cyperone. In this publication, studies involving hydroxylation of 2 by fungal cultures are presented. The resultant products are useful intermediates in efficient synthesis of eudesmane sesquiterpenes. Of five fungi tested, Rhizopus oryzae ATCC 11145 proved most versatile. It hydroxylates at the exocyclic C(11) position in high yield (70%) and, to a lesser extent, at C(5) (5%). Enzymatic activity appears at the end of growth phase and at least 2.2 g of 2 per liter can be metabolized without significant loss of product yield. A second fungus, Cunninghamella echinulata ATCC 9244, proved most useful for hydroxylation of derivatives of 2 for the preparation of derivatives of β -cyperone, although product yields were low (2–20%), some derivatives were nonreactive, and hydroxylation at C(9) occurred. The relationship between precursor structure and enzyme affinity is discussed. 相似文献
284.
285.
The evaluation of second derivatives of the electronic energy for nonvariational wave functions using an energy functional is discussed. It is shown that, in certain cases, the formation of the first-order relaxed density matrix leads to an efficient algorithm for the calculation of second-order response properties. Detailed formulas are given for second-order Møller–Plesset perturbation theory. © 1994 John Wiley & Sons, Inc. 相似文献
286.
287.
288.
The capability of gated saturable absorbers for single-pulse selection is studied theoretically using the classical space-time-dependent rate-equation model. The dynamics of operation is followed experimentally by the well-known pump—probe technique. Comparing the theoretical and experimental results, it is found that gated saturable absorbers can efficiently be used for pulse forming and pulse selection of pulses longer than picosecond. 相似文献
289.
The applicability of differential electrolytic potentiometry as a detection system in flow injection analysis is investigated. A computer-controlled injector which delivers precise volumes of sample solutions in a reproducible manner was developed. Conditions such as current density employed, the concentrations of the solutions used and the flow rate were optimized. Chloride in water was determined by means of this system. The relation between chloride concentration and the measured signal was found to be Nernstian for solutions of concentrations above 6 μg ml−1 chloride. For solutions below this concentration, the relation is linear. 相似文献
290.
V. A. Nebol'sin B. M. Darinskii E. E. Popova A. A. Shchetinin 《Russian Physics Journal》1995,38(10):1023-1026
An estimate of the factors which influence the rate of growth of filamentary silicon crystals in a standard chloride system using a quartz reactor with hot walls is given. It is shown that a diffusion form of crystallization is observed under the conditions investigated.Voronezh State Technical University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 10, pp. 22–26, October, 1995. 相似文献