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991.
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
992.
Xiao TL Tesarova E Anderson JL Egger M Armstrong DW 《Journal of separation science》2006,29(3):429-445
HPLC enantiomeric separations of a wide variety of racemic analytes was evaluated using chiral stationary phases (CSPs) based on the macrocyclic glycopeptides teicoplanin (T), teicoplanin aglycone (TAG), and methylated teicoplanin aglycone (Me-TAG) in two different mobile phase modes, i.e., the RP mode and the polar organic (PO) mode. Comparison of the enantiomeric separations using Chirobiotic T, Chirobiotic TAG, and the methylated form of TAG were conducted in order to gain a better understanding of the roles of the polar functional groups on the CSP. Substantial effects due to the cleavage of saccharides and/or methylation on chiral separations were observed in both separation modes. Improved separation efficiencies for many acidic analytes were obtained by methylating the H-bonding groups of TAG. These groups were believed to be a contributing factor to band broadening on TAG due to their negative effect on mass transfer between the stationary phase and mobile phase. Ionic/dipolar interactions between the carboxylate group of the analytes and the amine groups on T, TAG, or Me-TAG are important for chiral discrimination. Therefore, analytes possessing a carboxyl group are good candidates for successful separations on these CSPs. Hydrophobic interactions are important for enantiomeric separations in the RP mode where the H-bonding interactions between analytes and the chiral selectors are relatively weak. Me-TAG offers higher hydrophobicity, which can accentuate the interactions of analytes with hydrophobic moieties, but these interactions are not necessarily stereoselective. In the PO mobile phase, electrostatic/dipolar interactions between polar functional groups are the dominating interactions in chiral recognition. Another important factor is steric fit, which could be changed with every modification of the T structure. Therefore, substantial changes of enantioseparations were obtained within this studied group of CSPs. The PO mode was shown to be the most powerful mobile phase mode for enantiomeric separations on T-based stationary phases, mainly due to the improved efficiency. Methylation of the TAG proved to be a very useful tool for investigating the chiral recognition mechanism for this group of chiral selectors. 相似文献
993.
For the direct separation of enantiomers of tryptophan analogs, a native α-cyclodextrin-based Cyclobond III chiral stationary phase was examined. The separation conditions were optimized by variation of the different chromatographic parameters, and data are reported as retention factors, separation factors and resolutions. The nature and concentration of the buffers as mobile phase additivies exerted only slight effects on the retention and resolution. In all cases, the erythro isomers could be separated significantly better than the threo ones. With increasing hydrophobicity of the analytes, the retention time increased, but no clear trend could be observed between the resolution and the hydrophobicity. The sequence of elution of the enantiomers was in most cases determined by spiking the racemic samples with enantiorich analytes. 相似文献
994.
995.
S.P. Stewart S.E.J. Bell W.J. Armstrong G. Kee S.J. Speers 《Journal of Raman spectroscopy : JRS》2012,43(1):131-137
Multilayer samples of white architectural paint potentially have very high evidential value in forensic casework, because the probability that two unrelated samples will have the same sequence of layers is extremely low. However, discrimination between the different layers using optical microscopy is often difficult or impossible. Here, lateral scanning Raman spectroscopy has been used to chemically map the cross‐sections of multilayer white paint chips. It was found that the spectra did allow the different layers to be delineated on the basis of their spectral features. The boundaries between different layers were not as sharp as expected, with transitions occurring over length scales of > 20 µm, even with laser spot diameters < 4 µm. However, the blurring of the boundaries was not so large as to prevent recording and identification of spectra from each of the layers in the samples. This method clearly provides excellent discrimination between different multilayer white paint samples and can readily be incorporated into existing procedures for examination of paint transfer evidence. © 2011 Crown copyright. 相似文献
996.
997.
N. T. Zinner J. R. Armstrong A. G. Volosniev D. V. Fedorov A. S. Jensen 《Few-Body Systems》2012,53(3-4):369-385
We consider a bilayer setup with two parallel planes of cold fermionic polar molecules when the dipole moments are oriented perpendicular to the planes. The binding energy of two-body states with one polar molecule in each layer is determined and compared to various analytic approximation schemes in both coordinate- and momentum-space. The effective interaction of two bound dimers is obtained by integrating out the internal dimer bound state wave function and its robustness under analytical approximations is studied. Furthermore, we consider the effect of the background of other fermions on the dimer state through Pauli blocking, and discuss implications for the zero-temperature many-body phase diagram of this experimentally realizable system. 相似文献