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It has been suggested from QSAR data (P. D. Edwards, D. J. Wolanin, D.A. Andisik and M. W. Davis, J. Med. Chem., 1995, 38, 76) that the inhibition of elastase by peptidyl alpha-ketoheterocyclic inhibitors can occur in two ways, the less potent inhibitors forming a non-bonded Michaelis complex and the more potent set a covalently bonded enzyme-substrate intermediate. We report QM/MM studies of both binding and reactivity that confirm these findings, showing that the activity of the least potent set of inhibitors correlates with the calculated binding energy, and that of the more potent set correlates with the stability of the intermediate. These calculations show that QM/MM methods can be successfully employed to understand complicated structure-activity relationships and might be employed in the design and assessment of new inhibitors. 相似文献
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Abstract This paper considers how a low concentration (> 2 per cent w/w) of a photochrome dissolved in a liquid crystal affects the physical properties of the host mesogen. A novel class of photochromes, the fulgide based dyes, have been used to give a new approach in this area of study. Unlike many other light active dyes, the fulgides exhibit only a relatively small shape change. Because of this, the influence of the changes in the physical properties of the guest (for example, the dipole moment) are readily studied. Both thiophene and furan fulgide doped liquid crystal systems were studied in the irradiated and non-irradiated states and as a function of concentration. The changes in phase transition temperature, refractive index and order parameter for these various states as compared to the pure host liquid crystal have been measured to investigate the way in which the dye alters the mesomorphic properties of the host, on a molecular level. 相似文献
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Abstract The particular phase in which a liquid crystal system will exist is that which has the lowest free energy at a certain temperature. The free energy may depend on variables such as temperature, pressure, chirality, etc. One way in which the stability of a particular thermodynamic phase, relative to its neighbours, would be manifest is in its temperature range. The effect of chirality, in particular, on the temperature range or stability of blue phases has been well-studied both experimentally and theoretically. To date these studies assume that chirality is the only parameter which will influence the existence of blue phases. However, blue phases with relatively low chirality and broad range, which should in principle only show very narrow blue phases, have been reported. This suggests that factors other than chirality are involved in blue phase stability. In this paper we investigate the phase stability of various blue phase mixtures containing equal amounts of a chiral dopant, via their blue phase temperature range. Correlation between blue phase stability and the elastic constants k 2 and k 22, molecular length of the nematic host, and the order parameter at the blue phase to cholesteric transition is discussed. We have confirmed that for our mixtures the total blue phase temperature range may be related equally to the elastic constant k 22 and the chirality. We also present the first data displaying an odd-even effect in blue phases. Finally, we have found an apparent correlation between the stability of the blue phases and the magnitude of the orientational order parameter of the cholesteric phase at the cholesteric to blue phase transition. 相似文献
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S. V. Serak E. O. Arikainen H. F. Gleeson V. A. Grozhik J.-P. Guillou N. A. Usova 《Liquid crystals》2013,40(1):19-26
The isothermal formation of concentric colour domains has been observed in a cholesteric mixture doped with 10 wt % of a photochromic nematic material. The host cholesteric mixture included the Merck materials BL131a and BL130, while the photochromic dopant was a mixture of 4-n-butyl-4′-n-alkoxyazobenzenes (BAAB). The helical pitch of the host cholesteric mixture was increased, as expected, on addition of the photochromic nematic material prior to irradiation with the molecules in the purely trans-configuration. On irradiation with low power (0.6 mW) argon ion laser light, cis-isomers formed within the interaction region and concentric colour domains appeared. Selective reflection from the colour domains occurred in the 400–560 nm spectral range. The coloured domains persisted in the time period following irradiation and extended beyond the interaction region because of diffusion of the cis-isomers. Using the diffusion equation, an expression has been obtained for the average concentration of cis-isomers in each of the coloured domains and the dependence of the reflection wavelength upon the concentration of cis-isomers has been determined. 相似文献