Berthod A, Carda-Broch S
Laboratoire des Sciences Analytiques, CNRS, Université de Lyon 1, Bat CPE-308, 43 Boulevard du 11 November 1918, 69622 Villeurbanne Cedex, France.
J Chromatogr A. 2004 May 28;1037(1-2):3-14. doi: 10.1016/j.chroma.2004.01.001.
By essence, all kinds of chromatographic methods use the partitioning of solutes between a stationary and a mobile phase to separate them. Not surprisingly, separation methods are useful to determine accurately the liquid-liquid distribution constants, commonly called partition coefficient. After briefly recalling the thermodynamics of the partitioning of solutes between two liquid phases, the review lists the different methods of measurement in which chromatography is involved. The shake-flask method is described. The ease of the HPLC method is pointed out with its drawback: the correlation is very sensitive to congeneric effect. Microemulsion electrokinetic capillary electrophoresis has become a fast and reliable method commonly used in industry. Counter-current chromatography (CCC) is a liquid chromatography method that uses a liquid stationary phase. Since the CCC solute retention volumes are only depending on their partition coefficients, it is the method of choice for partition coefficient determination with any liquid system. It is shown that Ko/w, the octanol-water partition coefficients, are obtained by CCC within the -1 < log Ko/w < 4 range, without any correlation or standardization using octanol as the stationary phase. Examples of applications of the knowledge of liquid-liquid partition coefficient in the vast world of solvent extraction and hydrophobicity estimation are presented.
本质上，所有类型的色谱方法都是利用溶质在固定相和流动相之间的分配来实现分离。毫不奇怪，分离方法对于准确测定液-液分配常数（通常称为分配系数）很有用。在简要回顾了溶质在两个液相之间分配的热力学之后，本文综述列出了涉及色谱法的不同测量方法。描述了摇瓶法。指出了高效液相色谱法的简便性及其缺点：相关性对同系物效应非常敏感。微乳液电动毛细管电泳已成为工业上常用的一种快速可靠的方法。逆流色谱（CCC）是一种使用液体固定相的液相色谱方法。由于CCC溶质保留体积仅取决于它们的分配系数，因此它是用任何液体系统测定分配系数的首选方法。结果表明，通过CCC在-1 < log Ko/w < 4范围内获得正辛醇-水分配系数Ko/w，无需使用正辛醇作为固定相进行任何相关性或标准化处理。本文还介绍了液-液分配系数知识在溶剂萃取和疏水性估计这一广阔领域中的应用实例。
