Newman Carl I D, McGuffin Victoria L
Department of Chemistry, Michigan State University, East Lansing, MI 48824-1322, USA.
Electrophoresis. 2006 Feb;27(3):542-52. doi: 10.1002/elps.200500645.
The theoretical plate height model, extended to include reactive CE, is used to calculate equilibrium constants and rate constants for the reversible, first-order isomerization of proline dipeptides. This model is consistent with chromatographic theory and enables calculation of equilibrium constants from velocity and calculation of rate constants from plate height. Thermodynamic and kinetic parameters for isomerization of Ala-Pro and Phe-Pro are calculated by using the plate height model, and are shown to be in good agreement with literature values. Additionally, the efficacy of the plate height model is compared to ChromWin, an existing simulation method for calculating rate constants from zone profiles. It is shown that ChromWin and the plate height model are complementary methods. ChromWin is best used for calculating rate constants for reactions that are far from steady state, where the zone profiles exhibit plateau formation. On the other hand, the plate height model is best used for calculating rate constants for reactions that are at or near steady state, where the zone profiles exhibit a single zone containing both reacting species.
扩展到包括反应性毛细管电泳的理论塔板高度模型，用于计算脯氨酸二肽可逆一级异构化的平衡常数和速率常数。该模型与色谱理论一致，能够根据速度计算平衡常数，并根据塔板高度计算速率常数。通过使用塔板高度模型计算了丙氨酸 - 脯氨酸和苯丙氨酸 - 脯氨酸异构化的热力学和动力学参数，结果表明与文献值吻合良好。此外，将塔板高度模型的效能与ChromWin（一种现有的从区带图谱计算速率常数的模拟方法）进行了比较。结果表明，ChromWin和塔板高度模型是互补的方法。ChromWin最适合用于计算远离稳态的反应的速率常数，此时区带图谱会出现平台形成。另一方面，塔板高度模型最适合用于计算处于或接近稳态的反应的速率常数，此时区带图谱显示包含两种反应物种的单个区带。
