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1.
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3.
Based on thermodynamic analysis of interfacial segregation, the segregation enthalpy H
o of a solute I in a given matrix was found to depend linearly on two mutually independent terms reflecting the type of interface and the solid solubility limit X
infI
sup*
at temperature T and can be written as In this equation, the structural dependence of interfacial segregation is contained in H
*() which corresponds to the extrapolated segregation enthalpy of a solute with unlimited solubility in the matrix. The product [Tln(X
infI
sup*
)] is essentially constant with temperature, and can therefore be obtained from data for maximum solid solubility, [Tln(X
infI
sup*
)]max. The parameter v>0 represents the relationship between the activity a
infI
sup*
of a solute at the bulk solid solubility limit in a given matrix and X
infI
sup*
, a
infI
sup*
=(X
infI
sup*
)
v
, and is characteristic for the matrix. Using recent experimental data for silicon, phosphorus, and carbon segregation at well-characterized grain boundaries in oriented bicrystals of -iron, the averaged value
was determined. Values of H
*() range from -8 kJ/mol (general grain boundaries) up to +8 kJ/mol (special grain boundaries). These values are discussed and used for a more precise and generalized construction of grain boundary segregation diagrams of -iron. 相似文献
4.
Branislav Dugovi
Lubor Fiera MichalK. Cyranski Christian Hametner Nada Prnayov Marin Obranec 《Helvetica chimica acta》2005,88(6):1432-1443
The regio‐ and stereoselectivity of cycloadditions of the nitrone 1a and the chiral, sugar‐derived nitrones 13a and 13b with 3‐(prop‐2‐enoyl)‐1,3‐oxazolidin‐2‐one ( 2 ) depends on the nature of the Lewis acid catalyst used. Addition of Lewis acid reverses the regioselectivity of the cycloaddition, and improves the anti‐diastereoselectivity in the case of chiral nitrones. The sterically favored isoxazolidin‐5‐yl‐substituted adducts 3, 4 , and 14 – 17 are produced as the major products in the absence of Lewis acid, while the electronically favored regioisomers with isoxazolidin‐4‐yl substituents ( 5, 6 , and 18 – 21 , respectively) are obtained as major products in the [Ti(OiPr)2Cl2] catalyzed reactions. The reactions of nitrone 13b with 2 in the presence of other Lewis acids such as ZnCl2, ZnBr2, ZnI2 and MgI2/I2 gave both regioisomeric pairs of the diastereoisomers, favoring the 4‐substituted congeners. The diastereoisomeric isoxazolidines 3a – 6a were reduced with NaBH4 in THF/H2O with subsequent desilylation to yield the separable diols 9 – 12 . Reduction of the diastereoisomeric isoxazolidines 19a and 18a afforded the chiral alcohols 23 and 22 , the latter of which was analyzed by X‐ray crystallography. 相似文献
5.
Lubor Lejček 《Czechoslovak Journal of Physics》2000,50(10):1147-1158
The structure of a point defect in the director field near (–)-wedge disclination line singularity in a thick sample of a nematic liquid crystal is approximately described. The elastic interaction energy of two point defects of the opposite sign is evaluated. There is always the attraction between two opposite point defects, as expected. Nevertheless, with the defect separation their attraction force decreases. When the attraction force is of the same order as a viscous force acting against a free molecular rotation, the movement of point defects is very slow. For example, the defect separation at which the relative velocity of point defects is about 0.025 m/day was estimated as 160 m. 相似文献
6.
L. Lejček 《Czechoslovak Journal of Physics》1986,36(7):814-818
The influence of the finite dimension of a chiral smectic C liquid crystal planar sample on the helical pitch length is discussed. The discussion is based on the properties of the disclination PH2 system described in Czech. J. Phys. B35 (1985) 655. It is concluded that the existence of the sample free surface can lead to pitch changes with respect to the pitch of a perfect infinite chiral smectic C liquid crystal. 相似文献
7.
Glogarová M Hampl F Lejček L Novotná V Svoboda J Cigl M 《The Journal of chemical physics》2010,133(22):221102
For the first time, domains with twisted structures have been established in planar samples of achiral compounds in tilted smectic C phase. This evidences separation of molecular conformers differing in the sense of axial chirality and confirms polar C(2) symmetry of these domains. A simple model considering polar surface anchoring energy and bulk energy of the twist can account for this finding. Conditions for coexistence of twisted and homogeneous domains are discussed. 相似文献
8.
The development of molecular imaging agents with multiple functions has become a major trend in radiopharmaceutical chemistry. We present herein the syntheses of trifunctional compounds, combining an acridine orange (AO) based intercalator with a GRP receptor specific bombesin like peptide (BBN). Metal-mediated conjugation of these two functions via the [2 + 1] approach to the third function, the [M(CO)(3)](+) (M = (99m)Tc, Re) moiety, yielded the final trifunctional molecules. The strongly fluorescent acridine orange, a nuclear targeting agent, has been derivatised with 4-imidazolecarboxylate as a bidentate ligand and bombesin with an isonitrile group as a monodentate ligand. For cell and nuclear uptake studies, [Re(L(1)-BBN)(L(2)-Ical)(CO)(3)] type complexes were synthesized and characterized. For radiopharmaceutical purposes, the (99m)Tc analogues have been prepared in a stepwise synthesis. Fluorescence microscopy studies on PC-3 cells, bearing the BBN receptor, showed high and rapid uptake into the cytoplasm. For the bifunctional molecule, lacking the BBN peptide, no internalization was observed. 相似文献
9.
L. Lejček 《Czechoslovak Journal of Physics》1979,29(2):196-202
A class of solutions of a system of three Peierls-Nabarro equations is found using the methods of complex variable. These solutions could be used for investigation of non-planar screw dislocation cores within the Peierls-Nabarro model where the cores are dissociated along three intersecting slip planes. 相似文献
10.