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911.
Májek P Mydlová J Krupcík J Lehotay J Armstrong DW Cotton FA 《Journal of separation science》2006,29(15):2357-2364
A classical kinetic method was used to determine the energy barrier for the inter-conversion of 2,3-pentadienedioic acid enantiomers. Each individual enantiomer was isolated by collecting the appropriate peaks from the HPLC enantiomeric separation, of racemic 2,3-pentadienedioic acid. The isolated enantiomers were racemized at 22 degrees C using various interconversion times. The ratio of enantiomers in each reaction solution was determined by HPLC at 22 degrees C. The corresponding peak areas of the enantiomers and the interconversion times obtained from the HPLC chromatograms were used to calculate both the interconversion rate constants describing (+)--> (-) and (-) --> (+) interconversions as well as the energy barriers. It was confirmed that the interconversion of 2,3-pentadienedioic acid enantiomers is a firstorder kinetic reaction. Both semiempirical and ab initio methods were used to explore the mechanism of the interconversion of 2,3-pentadienedioic acid enantiomers, and to calculate the interconversion energy barrier. Comparison of the interconversion energy barriers found by the ab initio method (deltaG# = 110.7 kJ/mol) and by classical kinetics in the mobile phase solution at 22 degrees C (delta Gapp = 93.9+/-0.2 kJ/mol) shows a difference which may be attributed to the different conditions assumed in the theoretical calculation (i.e., a gaseous state) and the actual experimental conditions (i. e., liquid solution) and a possible catalytic effect of the solution composition. 相似文献
912.
Five end-capped octadecyl RP stationary phases, among which one was a polar embedded stationary phase, were tested for the analysis of benzoic acid derivatives using two mobile phases with or without addition of formic acid (water pH was measured by a common approach; pH of water with addition of formic acid was 3.0 and without formic acid 5.8). The influence of mobile-phase pH on the retention of benzoic acid derivatives was under study. Consequently, Purospher-STAR and Alltima columns provided symmetrical peaks for benzoic acid derivatives at pH 3.0 and also at pH 5.8. Reprosil and Symmetry stationary phases showed poor peak shapes at higher pH of the mobile phase. Differences between the tested columns may be caused by surface heterogeneity. Another reason may be the presence of some atoms creating additional adsorption sites on the surface of Reprosil and Symmetry stationary phases. This can lead to enhanced silanol activity resulting in peak tailing. The addition of formic acid into the mobile phase improved peak shapes. The polar embedded C18 stationary-phase Synergi-Fusion-RP appeared as not a suitable column for the analysis of benzoic acid derivatives. Synergi-Fusion-RP provided asymmetrical peaks even if formic acid was added into the mobile phase. 相似文献
913.
A stereoselective approach has been developed to the new sugar amino acid and potential potent turn mimic 5-O-(tert-butyldimethylsilyl)-3-deoxy-1,2-O-isopropylidene-3-methoxycarbonylamino-alpha-D-xylofuranose 3-C-carboxylic acid (12), via the [3,3]-sigmatropic rearrangement of allylic thiocyanates (Z)-6 and (E)-7, prepared from D-xylose. The synthesis of a new dipeptide 13 is also described. 相似文献
914.
[reaction, structure: see text] A chemo- and regioselective copper-catalyzed cross-coupling reaction for effective amination of 2-chlorobenzoic acids with aniline derivatives has been developed. The method eliminates the need for acid protection and produces a wide range of N-aryl anthranilic acid derivatives in up to 99% yield. The amination was found to proceed with both electron-rich and electron-deficient aryl chlorides and anilines and also utilizes sterically hindered anilines such as 2,6-dimethylaniline and 2-tert-butylaniline. The conformational isomerism of appropriately substituted N-aryl anthranilic acids has been investigated in the solid state. Crystallographic analysis of seven anthranilic acid derivatives showed formation of two distinct supramolecular architectures exhibiting trans-anti and unprecedented trans-syn dimeric structures. 相似文献
915.
A chemo- and regioselective copper-catalyzed cross-coupling procedure for amination of 2-bromobenzoic acids is described. The method eliminates the need for acid protection and produces N-aryl and N-alkyl anthranilic acid derivatives in up to 99% yield. N-(1-Pyrene)anthranilic acid has been employed in metal ion-selective fluorosensing. Titration experiments showed that this pyrene-derived amino acid forms an equimolar complex with Hg(II) in water resulting in selective fluorescence quenching even in the presence of other metal ions such as Zn(II) and Cd(II). 相似文献
916.
In our paper we investigated the initial-boundary value problem for elastic layer situated on half space of another elastic medium. In this medium the thermomechanical interactions were taken into consideration. The system of equations with initial-boundary conditions describes the phenomenon of wave propagation with finite speed. In our problem there are two surfaces ie. free surface and contact surface between layer and half space. On the free surface are setting boundary conditions for normal and tangent surface force. We consider two types of contact between layer and half-space: rigid contact and slip contact. The initial-boundary value problem was solved by using integral transformations and Cagniard-de Hoope methods. From the solution of this problem follows that in layer and half space exist some kind of thermoelastic waves. We investigated moreover the conditions which should be fullfiled for propagation of Rayleigh and Love's type waves on the contact surface between layers and half space. The results obtained in our investigation were used in technical applications especially engineering design and diagnostics of roads and airfields. (© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
917.
In spite of attention devoted to molecular mechanisms of apoptosis, the details of functioning of one crucial component–the Bcl-2 apoptotic switch–are not completely understood. There are two competing mechanisms of its internal working—the indirect activation and the direct activation. In the absence of conclusive experimental data, we have used computational modeling to assess the properties of both mechanisms and their suitability to act as a biological switch. Since the two mechanisms form opposite poles of continuum of Bcl-2 molecular interaction models, we have constructed more general models including these two models as extreme cases. By studying the relationship between model parameters and the steady-state response we have found optimal interaction patterns which reproduce the behavior of the Bcl-2 apoptotic switch. Our results show, that stimulus–response ultrasensitivity is negatively affected by spontaneous activation of Bcl-2 effectors. We found that ultrasensitivity requires effectors activation, mediated by another subgroup of Bcl-2 proteins—activators. We have shown that the auto-activation of monomeric effector forms provides an ultrasensitivity enhancing feedback loop. Thorough robustness analysis revealed that the interaction pattern postulated in the direct activation hypothesis is able to conserve stimulus–response switching characteristics for wide range changes of its internal parameters. The robustness of the switch against the variation of the reaction parameter is strongly reduced for the intermediate hybrid model and even more for the indirect part of the models. Computer simulations of the more general model presented here suggest, that stimulus–response ultrasensitivity is an emergent property of the direct activation model that is unlikely to occur in the model of indirect activation. Introduction of indirect-model-specific interactions does not provide a better explanation of the Bcl-2 switch functionality compared to the direct model. 相似文献
918.
Jozef Kaiser Karel Novotný Madhavi Z. Martin Aleš Hrdlička Radomír Malina Martin Hartl Vojtěch Adam René Kizek 《Surface Science Reports》2012,67(11-12):233-243
Laser-Induced Breakdown Spectroscopy (LIBS) is a sensitive optical technique capable of fast multi-elemental analysis of solid, gaseous and liquid samples. Since the late 1980s LIBS became visible in the analytical atomic spectroscopy scene; its applications having been developed continuously since then. In this paper, the use of LIBS for trace element determination in different matrices is reviewed. The main emphasis is on spatially resolved analysis of microbiological, plant and animal samples. 相似文献
919.
920.
Dr. August Chwala 《Colloid and polymer science》1931,55(2):251-254
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