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211.
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
212.
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
213.
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
214.
A. Hagfeldt S. Lunell H. O. G. Sieghbahn 《International journal of quantum chemistry》1994,49(2):97-104
The energy levels of small titanium oxide clusters [(TiO2)2, and (TiO2H)3, and (TiO2H)2] have been calculated using ab initio SCF methods. Both crystal and relaxed geometries have been considered. Systematic changes in the valencelevel structure resulting from geometry relaxation are found, which may be related to band-gap changes experimentally observed for small titanium oxide particles. In addition, a Ti? OH local surface state is found to be well described within a limited cluster model. © 1994 John Wiley & Sons, Inc. 相似文献
215.
A set of exact conditions is compiled for the purpose of developing and testing approximations for the exchange-correlation energy as a functional of the electron density. Special emphasis is placed upon recently developed density-scaling relationships. Commonly used generalized gradient approximations are compared against several of these conditions. A direct tabular comparison of these functionals (not of calculated properties) with one another is also made. © 1994 John Wiley & Sons, Inc. 相似文献
216.
217.
218.
E. N. Yurchenko G. E. Kramareva N. G. Zubritskaya T. P. Gaidei 《Reaction Kinetics and Catalysis Letters》1995,55(2):425-432
In the Russian Scientific Center Applied Chemistry catalysts have been developed for the gas-phase fluorination of organics, including chlorine-containing substances, hydrogenation and reductive amination of organic substances, decomposition of liquid substances to gases, complete oxidation and reduction, suitable for environment at protection. 相似文献
219.
220.
Summary This paper is concerned with the problem of developing numerical integration algorithms for differential equations that, when
viewed as equations in some Euclidean space, naturally evolve on some embedded submanifold. It is desired to construct algorithms
whose iterates also evolve on the same manifold. These algorithms can therefore be viewed as integrating ordinary differential
equations on manifolds. The basic method “decouples” the computation of flows on the submanifold from the numerical integration
process. It is shown that two classes of single-step and multistep algorithms can be posed and analyzed theoretically, using
the concept of “freezing” the coefficients of differential operators obtained from the defining vector field. Explicit third-order
algorithms are derived, with additional equations augmenting those of their classical counterparts, obtained from “obstructions”
defined by nonvanishing Lie brackets. 相似文献