Interdisciplinary Center for Nanotoxicity, Department of Chemistry and Biochemistry, Jackson State University, Jackson, MS 39217, USA.
Chirality. 2012 Jan;24(1):72-7. doi: 10.1002/chir.21028. Epub 2011 Nov 26.
In this work, the enantioseparation of 15 structurally similar chiral solutes is studied, and analysis of the retention factors is performed using a genetic algorithm and multiple linear regression analysis technique. The present quantitative structure-enantioselective retention relationship model generated for retention factors' data has confirmed the importance of a number of descriptors altering the retention behavior and enantioselectivity of the studied compounds. Thus, fragment-based descriptor PSA, which encodes polar surface area, has confirmed the crucial role of heteroatoms in the retention behavior exhibited by pyrroliddin-2-ones. The presence of E(LUMO) descriptor, which represents a quantum-chemical property, has indicated the role of charge transfer interactions between the chiral stationary phase and enantiomers to retention factors, showing that lowest unoccupied molecular orbital energy is significantly different between enantiomers. The developed model exhibits a very good performance characterized by following statistical parameters: r(2) = 0.93 for training set and r(2) = 0.99 for the validation set. The selected three-variable model displays high predictive ability, catching the main factors affecting the enantioselectivity of studied chiral compounds, and therefore can be used for prediction of retention factors of other chiral compounds of similar structure to improve the separation process and so on.
在这项工作中，研究了 15 种结构相似的手性溶质的对映体分离，并使用遗传算法和多元线性回归分析技术对保留因子进行了分析。为保留因子数据生成的现有定量构效关系-对映选择性保留关系模型，证实了改变研究化合物保留行为和对映选择性的许多描述符的重要性。因此，基于片段的描述符 PSA（编码极性表面积）证实了杂原子在手性固定相和对映体之间的保留行为中所起的关键作用。存在 E(LUMO)描述符，它表示量子化学性质，表明手性固定相和对映体之间的电荷转移相互作用对保留因子的作用，表明最低未占据分子轨道能量在对映体之间有显著差异。所开发的模型具有非常好的性能，其统计参数如下：训练集的 r(2) = 0.93，验证集的 r(2) = 0.99。所选的三变量模型具有较高的预测能力，捕捉到影响研究手性化合物对映选择性的主要因素，因此可用于预测其他类似结构的手性化合物的保留因子，以改进分离过程等。
