García-Lopera Rosa, Irurzun Isabel, Abad Concepción, Campos Agustín
Department de Química Física and Institut de Ciéncia dels Materials, Universitat de València, E-46100 Burjassot, València, Spain.
J Chromatogr A. 2003 May 9;996(1-2):33-43. doi: 10.1016/s0021-9673(03)00609-5.
The elution behaviour of different polymer-solvent systems in three types of organic columns for SEC has been compared and interpreted. The experimental data show that the classical universal calibration is not accomplished. Deviations from a unique curve are observed due to the binary and ternary interactions between the components of the system (solvent, polymer and gel) which results on secondary mechanisms accompanying the main pure or "ideal" SEC separation mechanism. Both, enthalpic and entropic effects are interpreted in terms of the swelling and crosslinking degrees of the gel packings, and are also related with the fractal characteristics of their surfaces, such as the fractal dimension and the available pore size. Moreover, a relationship between the fractal dimension of the pore surface and the chromatographic distribution coefficient is proposed.
比较并解释了不同聚合物 - 溶剂体系在三种用于尺寸排阻色谱(SEC)的有机柱中的洗脱行为。实验数据表明,经典的普适校准并未实现。由于体系(溶剂、聚合物和凝胶)各组分之间的二元和三元相互作用,观察到与唯一曲线的偏差,这导致了伴随主要的纯或“理想”SEC分离机制的二级机制。焓效应和熵效应均根据凝胶填料的溶胀和交联程度进行解释,并且还与它们表面的分形特征相关,如分形维数和可用孔径。此外,还提出了孔表面分形维数与色谱分配系数之间的关系。