Ahmed Al-Haj M, Kaliszan R, Buszewski B
Department of Biopharmaceutics and Pharmacodynamics, Medical University of Gdansk, Poland.
J Chromatogr Sci. 2001 Jan;39(1):29-38. doi: 10.1093/chromsci/39.1.29.
The performance of several previously designed model series of test analytes has been tested to characterize in an objective, quantitative manner modern stationary phases for reversed-phase high-performance liquid chromatography (RP-HPLC) using quantitative structure-retention relationships (QSRRs). Three QSRR approaches and three respective series of test analytes recommended for studies of the molecular mechanism of chromatographic retention are employed: the reduced linear solvation energy relationship (LSER)-based model of Abraham, a model employing structural descriptors from molecular modeling, and a model relating retention to the n-octanol-water partition coefficient log P. All of the models and test analytes proposed provide reliable QSRR equations. Those equations discriminate in quantitative terms individual columns and chromatographic systems and can be interpreted in straightforward rational chemical categories. In view of QSRRs, the differences in the intermolecular interactions between a given stationary phase and a structurally defined analyte rationalize the observed differences in retention. The QSRR models (previously derived retrospectively) are demonstrated to work well on new sets of RP-HPLC data. At the same time, it has been confirmed that the three test series of analytes have properly been designed and can be recommended for comparative studies of analytical columns. QSRRs once derived on a given column for model analytes can be used to predict the retention of other analytes of a defined structure. That in turn can facilitate the procedure of the rational optimization of chromatographic separations.
已对几个先前设计的测试分析物模型系列的性能进行了测试，以便使用定量结构保留关系（QSRR）以客观、定量的方式表征用于反相高效液相色谱（RP-HPLC）的现代固定相。采用了三种QSRR方法以及为研究色谱保留分子机制而推荐的三个相应的测试分析物系列：基于简化线性溶剂化能关系（LSER）的亚伯拉罕模型、采用分子建模结构描述符的模型以及将保留与正辛醇-水分配系数log P相关联的模型。所提出的所有模型和测试分析物都提供了可靠的QSRR方程。这些方程在定量方面区分了各个色谱柱和色谱系统，并且可以用直接合理的化学类别进行解释。鉴于QSRR，给定固定相与结构明确的分析物之间分子间相互作用的差异使观察到的保留差异合理化。已证明QSRR模型（先前通过回顾性推导得出）在新的RP-HPLC数据集上效果良好。同时，已证实这三个分析物测试系列设计得当，可推荐用于分析柱的比较研究。一旦在给定色谱柱上为模型分析物推导得出QSRR，就可用于预测其他具有确定结构的分析物的保留情况。这反过来又可以促进色谱分离合理优化的过程。
