Accurate determination of log k'w in reversed-phase liquid chromatography. Implications for quantitative structure-retention relationships.
Accurate determination of log k'w in reversed-phase liquid chromatography. Implications for quantitative structure-retention relationships.
复制标题
反相液相色谱中 log kw 的准确测定。
DOI：
10.1016/0021-9673(93)80507-5
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发表时间：
1993
期刊：
影响因子：
--
通讯作者：
Dorsey,JG
中科院分区：
文献类型：
--
作者：
Hsieh,MM;Dorsey,JG
随着对反相液相色谱保留机制的了解不断加深，该技术越来越多地用于测量物理化学数据，尤其是可用于定量结构-活性关系的分区信息。然而，使用色谱保留需要选择一组标准的流动相条件。选择 100% 水具有理论上的优势，因为水相膜相是最常见的建模系统。然而，对于大多数实际溶质来说，用这种流动相实验测量 k' 值是困难或不可能的。人们已经提出了针对 100% 水的各种保留外推方法，但在比较时，对于相同的溶质通常会产生不同的值。大多数外推方法仅基于保留率与流动相的函数关系。然而，由于保留是通过流动相和固定相之间的溶质分配来控制的，因此不能忽略固定相的影响。本文将不同方法推算出的 logk′w 值与测量值进行了比较。 logk′w 的预测是根据作为流动相和固定相的函数的保留值来预测的。溶剂变色分析用于解卷积固定相和流动相的影响。建议从 ET(30) 图推断的 Logk′w 值作为定量结构保留关系最有意义的保留表示。
With increased understanding of the retention mechanisms of reversed-phase LC has come increased usage of the technique for the measurement of physico-chemical data, especially partitioning information that can be used for quantitative structure—activity relationships. However, the use of chromatographic retention requires that a standard set of mobile phase conditions be chosen. The choice of 100% water has theoretical advantages, as an aqueous phase—membrane phase is the most common system being modeled. However, experimental measurement ofk′ values with this mobile phase is difficult or impossible for most real solutes. Various retention extrapolation methods to 100% water have been proposed, but when compared, often yield different values for the same solute. Most of the extrapolation methods are based on the retention as a function of the mobile phase only. However, as the retention is controlled by solute partitioning between the mobile phase and stationary phase, stationary phase effects cannot be ignored. In this paper logk′wvalues extrapolated from different methods are compared to the measured values. Prediction of logk′w, is attempted from the retention as a function of both the mobile phase and stationary phase. Solvatochromic analysis is used to deconvolute stationary and mobile phase effects. Logk′wvalues extrapolated fromET(30) plots are recommended as the most meaningful representation of retention for quantitative structure—retention relationships.