Poole Colin F, Poole Salwa K
Department of Chemistry, Wayne State University, Detroit, MI 48202, USA.
J Chromatogr A. 2009 Mar 6;1216(10):1530-50. doi: 10.1016/j.chroma.2008.10.092. Epub 2008 Oct 31.
The connection between the observable output in column chromatography (retention time, retention volume, retention factor, separation factor, etc.) and system properties (hold-up volume, pressure, temperature, isotherm behavior, etc.) is discussed from a practical and mechanistic perspective for gas-liquid chromatography, reversed-phase liquid chromatography, supercritical fluid chromatography, micellar electrokinetic chromatography, and capillary electrochromatography. The unifying feature of these techniques is that retention can be described by a partition model, although not always exclusively. When over simplistic system models are used to explain variation in retention parameters they frequently mask the true reasons for poor repeatability and difficulties in transfer between system. Methods employing relative retention afford higher precision but may contain residual uncorrected errors. For those systems with several separate mechanisms contributing to retention the effective retention parameters can no longer be interpreted by simple partition models. The broadly based and practically focused material in this article affords an illustration of the often complicated relationship between system properties and retention, and the dangers that lurk in simplified retention models if the validity of their underlining approximations is not appropriate for the system under study.
从实践和机理的角度讨论了气相色谱、反相液相色谱、超临界流体色谱、胶束电动色谱和毛细管电色谱中柱色谱的可观测输出（保留时间、保留体积、保留因子、分离因子等）与系统特性（死体积、压力、温度、等温线行为等）之间的联系。这些技术的统一特点是保留可以用分配模型来描述，尽管并非总是唯一的。当使用过于简单的系统模型来解释保留参数的变化时，它们常常掩盖了重复性差和系统间转移困难的真正原因。采用相对保留的方法具有更高的精度，但可能包含残留的未校正误差。对于那些有几种独立机制影响保留的系统，有效的保留参数不再能用简单的分配模型来解释。本文内容广泛且注重实践，说明了系统特性与保留之间通常复杂的关系，以及如果简化保留模型的基础近似有效性不适用于所研究的系统，其中潜藏的危险。
