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101.
Matthias Heydenreich Andreas Koch E. Kleinpeter Thomas Zimmermann 《Fresenius' Journal of Analytical Chemistry》1997,357(5):517-521
Dynamic NMR investigations of a number of 2-amino-3-aroyl-4,6-diaryl-pyrylium salts were carried out. The barrier to rotation
of the partial C, N double bond was determined and proved to be in the range of 62 to 63 kJ/mol. Quantum chemical calculations
of bond orders and electron densities of the different atoms in the molecules show the distinct double bond character of the
exocyclic C, N bond. This is in agreement with the relatively high barrier to rotation. By quantum chemical ab initio 3-21G
calculations, the dynamic behaviour of this kind of compounds was simulated; two pairs (image and mirror image) of ground
state conformations, in coincidence with the experiment, were obtained.
Received: 10 May 1996 / Revised: 1 July 1996 / Accepted: 4 July 1996 相似文献
102.
Transition temperatures (TN1) from the nematic lyotropic liquid-crystalline phase to the isotropic phase were measured for the system cetyltrimethylammonium bromide (CTAB) water in the presence of small amounts of 3-stilbene carboxylic acid (3SC), 4-stilbene carboxylic acid (4SC) and Δ2/2'-bi-(2H-l,4-benzothiazine) (BT). TNI, increases as a function of trans-3SC or trans-4SC concentration, ranging from 01 to 08 wt %, by up to 12°C. A further increase in TNI between 2 and 5°C can be achieved by photochemically converting the solubilized trans stilbene derivatives to the cis isomers. Irradiation of a trans-3SC containing sample at a temperature just above TNl leads to a light-induced phase transition to the lyotropic liquid-crystalline phase. Solubilization of trans-BT causes a slight decrease of TNI while photoisomerization to cis-BT increases TNI by 1°C. 相似文献
103.
The synthesis and complexation properties of 1,4-dimethyl-8-[2-(2-pyridyl)ethyl]-1,4,8,11-tetraazacyclotetra-decane ( 2 ) are described. This ligand forms with Cu2+ two complexes, one of which has been characterized by X-ray structure analysis. The structural, spectral, and kinetic studies indicate that the two Cu2+ complexes are isomers with the macrocycle in the trans-III and trans-I configuration. The rate of the interconversion of the trans-I isomer to the thermodynamically more stable trans-III species is proportional to [OH?]. A mechanism for this reaction is proposed. 相似文献
104.
105.
Thomas B. Grimley 《Theoretical chemistry accounts》1987,72(5-6):475-484
A model for one-phonon thermal desorption is presented in which the structure of the substrate phonons, expressed as a projection on a surface atom of the phonon density of states, appears as a separate factor in the angle- and energy-resolved desorption rate. Desorption from both localized, and delocalized initioladatom states is considered. Under certain circumstances one can obtain the cosine-distribution of the equilibrium theory, but in general, the desorption flux from delocalized states deviates from the cosine law by being peaked away from the surface normal, whereas for localized initiol states, the flux is concentrated more in the normal direction. 相似文献
106.
107.
We study the transversal spin–spin correlations in the non-equilibrium steady state of the XY chain constructed by coupling a finite cutout of the chain to the two infinite parts to its left and right acting as thermal reservoirs at different temperatures. We prove that the spatial decay of these correlations is at least exponentially fast. 相似文献
108.
Jean-Marie Lehn 《Journal of Chemical Sciences》1994,106(5):915-922
The article discusses molecular recognition and overviews the key concepts -storage and retrieval of chemical information
by molecular structures, supramolecular reagents and catalysts, molecular transport, semiochemistry and self assembly. The
prospects of controlling supramolecular architecture through engineered molecular recognition and design of ‘programmed systems’
controlled by molecular information are also discussed. 相似文献
109.
110.