Kaliszan R, van Straten M A, Markuszewski M, Cramers C A, Claessens H A
Department of Biopharmaceutics and Pharmacodynamics, Medical University of Gdańsk, Poland.
J Chromatogr A. 1999 Sep 10;855(2):455-86. doi: 10.1016/s0021-9673(99)00742-6.
Quantitative structure-retention relationships (QSRRs) were derived for logarithms of retention factors normalised to a hypothetical zero percent organic modifier eluent, log kw, determined on 18 reversed-phase high-performance liquid chromatography (RP-HPLC) columns for 25 carefully designed, structurally diverse test analytes. The study was aimed at elucidating molecular mechanism of retention and at finding an objective manner of quantitative comparison of retention properties and classification of modern stationary phases for RP-HPLC. Three QSRR approaches were employed: (i) relating log kw to logarithms of octanol-water partition coefficient (log P); (ii) describing log kw in terms of linear solvation-energy relationship-based parameters of Abraham; (iii) regressing log kw against simple structural descriptors acquired by calculation chemistry. All the approaches produced statistically significant and physically interpretable QSRRs. By means of QSRRs the stationary phase materials were classified according to the prevailing intermolecular interactions in the separation process. Hydrophobic properties of the columns tested were parametrized. Abilities of individual phases to provide contributions to the overall retention due to non-polar London-type intermolecular interactions were quantified. Measures of hydrogen-bond donor activity and dipolarity of stationary phases are proposed along with two other phase polarity parameters. The parameters proposed quantitatively characterize the RP-HPLC stationary phases and provide a rational explanation for the differences in retention patterns of individual columns observed when applying the conventional empirical testing methods.
针对25种精心设计、结构各异的测试分析物，在18根反相高效液相色谱（RP-HPLC）柱上测定了保留因子对数（以假设的零有机改性剂洗脱液归一化，即log kw），并推导了定量结构-保留关系（QSRR）。该研究旨在阐明保留的分子机制，寻找一种客观的方法来定量比较保留特性，并对RP-HPLC的现代固定相进行分类。采用了三种QSRR方法：（i）将log kw与正辛醇-水分配系数对数（log P）相关联；（ii）用基于线性溶剂化能关系的亚伯拉罕参数描述log kw；（iii）将log kw与通过计算化学获得的简单结构描述符进行回归分析。所有方法都得出了具有统计学意义且可物理解释的QSRR。借助QSRR，根据分离过程中主要的分子间相互作用对固定相材料进行了分类。对测试柱的疏水性能进行了参数化。量化了各固定相由于非极性伦敦型分子间相互作用对整体保留的贡献能力。提出了固定相的氢键供体活性和偶极矩的度量方法以及另外两个相极性参数。所提出的参数对RP-HPLC固定相进行了定量表征，并为应用传统经验测试方法时观察到的各柱保留模式差异提供了合理的解释。
