Relationship between the time-dependence of a transient-state kinetic isotope effect and the location of complexes in a reaction sequence.
Relationship between the time-dependence of a transient-state kinetic isotope effect and the location of complexes in a reaction sequence.
复制标题
瞬态动力学同位素效应的时间依赖性与反应序列中配合物的位置之间的关系。
DOI：
10.1021/jp057254x
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发表时间：
2006
期刊：
影响因子：
--
通讯作者：
Indyk,Lawrence
中科院分区：
文献类型：
--
作者：
Fisher,HarveyF;Palfey,BruceA;Maniscalco,StevenJ;Indyk,Lawrence
我们在这里证明了一个新的瞬态动力学规则，该规则指出，动力学同位素效应时间过程的一阶导数的比率，外推到零时间，提供积分值，指定在反应序列中的精确步骤数在单一的同位素取代反应。这条规则定义了这样的绝对值，即使在所涉及的步骤太快而无法提供可测量的中间体浓度以及整个反应顺序未知的情况下。
We prove here a new transient-state kinetic rule which states that the ratios of the first derivatives of kinetic isotope effect time courses, extrapolated to zero time, provide integral values which specify the precise step number in the reaction sequence in single isotope substituted reactions. This rule defines such absolute numbers even where the steps involved are too fast to provide measurable concentrations of intermediates and when the full reaction sequence is unknown.