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首页> 外文期刊>Electrophoresis: The Official Journal of the International Electrophoresis Society >The unified equation for the evaluation of degenerated first-order reactions in dynamic electrophoresis
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The unified equation for the evaluation of degenerated first-order reactions in dynamic electrophoresis

机译:评估动态电泳中退化的一阶反应的统一方程式

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摘要

An analytical solution for the unified equation for degenerated (pseudo-) first-order reactions, e.g., enantiornerization processes, in dynamic CE is presented, and validated with a dataset of 31 250 elution profiles covering typical experimental parameters. The unified equation was applied to determine the enantiornerization barrier of the hypnotic glutarimide derivative thalidomide (Contergan (R)) by dynamic capillary electrokinetic chromatography (DEKC). The enantiomer separation of thalidomide was performed in an aqueous 50 mM sodium borate buffer at pH 9.3 in the presence of the chiral mobile phase additive carboxymethyl-p-CD. Interconversion profiles featuring pronounced plateau formation were observed. Activation parameters Delta H-not equal and Delta S-not equal were obtained from temperature-dependent measurements between 20.0 and 37.5 degrees C in 2.5K steps. From the activation parameters the enantiornerization barrier of thalidomide at 37 degrees C under basic conditions were calculated to be Delta G(not equal) = 93.2 kJ/mol. Comparison of the kinetic data with results obtained at pH 8.0 reveals the catalytic influence of the base on the enantionnerization barrier.
机译:提出了动态CE中用于简并(伪)一阶反应(例如对映异构化过程)的统一方程的解析解,并使用涵盖典型实验参数的31 250个洗脱曲线的数据集进行了验证。通过动态毛细管电动色谱法(DEKC),使用统一方程式确定催眠戊二酰亚胺衍生物沙利度胺(Contergan(R))的对映异构化障碍。在手性流动相添加剂羧甲基-p-CD的存在下,在pH 9.3的50 mM硼酸钠水溶液中进行沙利度胺的对映异构体分离。观察到以明显的平台形成为特征的相互转化曲线。激活参数Delta H-不等于和Delta S-不等于是从温度依存的测量值在20.0到37.5摄氏度之间以2.5K的步长获得的。根据活化参数,在37℃下基本条件下沙利度胺的对映异构化势垒被计算为ΔG(不等于)= 93.2kJ / mol。将动力学数据与在pH 8.0下获得的结果进行比较,揭示了碱对对映体化屏障的催化作用。

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