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11.
A stochastic (Monte Carlo) simulation is used to investigate thermodynamic and kinetic contributions from the reversible A <--> B reaction in capillary electrophoresis (CE). The effects of equilibrium constant, rate constant, and electrophoretic mobility on the molecular zone profiles and the corresponding statistical moments are evaluated. As the reaction approaches steady state, the velocity of the zone is governed by the equilibrium constant and the electrophoretic mobilities of the reacting molecules. When the equilibrium constant is less than unity, the mean zone velocity is more similar to that of the reactant A. Conversely, when the equilibrium constant is greater than unity, the velocity is more similar to that of the product B. The extent of zone-broadening and asymmetry at steady state is dependent upon the equilibrium constant, the characteristic reaction lifetime, and the electrophoretic mobility difference between reacting molecules. If all other parameters are held constant, the plate height is greatest and skew is least when the equilibrium constant is unity. The plate height increases linearly with the characteristic reaction lifetime and electrophoretic mobility difference, whereas the skew is independent of these parameters. These conclusions have important implications for the elucidation of thermodynamic and kinetic information from experimental data. 相似文献
12.
Carbon-13 NMR methods were used to monitor changes in the proportions of crystalline and non-crystalline cellulose, and the exposure of chains on crystallite surfaces, in samples of alkali-treated kraft pulp and regenerated cellulose. A large increase in the amount of disorderd cellulose, as a result of conversion to cellulose II, is the major effect of alkali treatment with kraft pulp. Removal of small crystallites is the major effect with regenerated cellulose. Samples were examined never-dried, or were vacuum-dried prior to remoistening for characterization. Changes in molecular ordering consistent with pore collapse and coalescence of crystallite surfaces accompanied the removal of water. 相似文献
13.
Using a theory recently developed for the interpretation of activity coefficients of 1:1 electrolytes up to high concentrations in aqueous solution at 25°C, we have analysed available data for aqueous sodium chloride solutions up to saturation in the temperature range 273.15–573.15 K. The approach, which is based on Kirkwood-Buff theory and uses the truncated Poisson-Boltzmann equation to obtain the required information about the various ion-ion radial distributions, is able to fit the results to high accuracy with minimum of parameters, viz, three, of which one is the distance of closest approach, the other two relate to ion-solvent interactions and/or higher order terms in the ion-ion interaction. 相似文献
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We present a new formulation of a class of growth models-those which evolve according to an exclusion process. This formulation is based upon a transformation of the probability distribution function which involves Grassmann variables. This method is very general and enables one to derive an exact stochastic differential equation for the model of interest. We describe this method using the traffic model as an example. 相似文献
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Herein we report a new preparation of 4-hydroxy-2,5-dimethyl-2,3-dihydrofuran-3-one, the flavor compound strawberry furanone, based on a ‘green’ approach with a minimum number of steps. The first step is an enzymatic dioxygenation of p-xylene to form cyclohexadiene-cis-diol, followed by ring opening via ozonolysis, and ring closure to form the furanone. In efforts to improve the efficiency of the enzymatic step, a directed evolution approach was taken to increase the substrate specificity and selectivity of the toluene dioxygenase enzyme system. 相似文献
19.
All nondiverging algebraically special -spaces are found by means of the complexified spin-coefficient formalism. The solutions are found to group naturally into two classes according to whether or not the optical-rotation spin coefficient
vanishes.Research supported in part by a grant from the National Science Foundation. 相似文献
20.
H. Kurreck S. Aguirre H. Dieks J. Gtschmann J. v. Gersdorff H. Newman H. Schubert M. Speck T. Stabingis J. Sobek P. Tian A. Wiehe 《Radiation Physics and Chemistry》1995,45(6):853-865
Porphyrin quinones (P-Qs), covalently linked via different aliphatic bridges, have been synthesized and studies in their (porphyrin) cationic and (semiquinone) anionic radical states by EPR, ENDOR and TRIPLE resonance techniques. Electron transfer (ET) from the porphyrin donor to the quinone acceptor could be observed by time-resolved picosecond fluorescence spectroscopy (singlet ET) and by time-resolved EPR spectroscopy (triplet ET) in isotropic fluid solution and in anisotropic media (liquid crystals and reversed micelles). Steady-state in situ photoexcitation of P-Qs in CTAB cationic reversed micelles yielded the corresponding semiquinone radical anions. In TRITON X-100 reversed micelles both the radical cation of the porphyrin and the radical anion of the semiquinone could be detected, which occured in complete emission. In covalently linked porphyrin flavins ET from the photoexcited porphyrin fragment to the flavin and, in addition, energy transfer from the photoexcited flavin to the porphyrin could be observed. 相似文献