Quantitative structure-retention relationship studies using immobilized artificial membrane chromatography I: Amended linear solvation energy relationships with the introduction of a molecular electronic factor
Quantitative structure-retention relationship studies using immobilized artificial membrane chromatography I: Amended linear solvation energy relationships with the introduction of a molecular electronic factor
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DOI：
10.1016/j.chroma.2006.07.073
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发表时间：
2006-11-03
影响因子：
4.1
通讯作者：
He, Zhonggui
中科院分区：
文献类型：
--
作者：
Li, Jie;Sun, Jin;He, Zhonggui
通过引入分子电子因子修正的线性溶剂化能关系（LSERs），利用固定化人工膜（IAM）色谱，特别是可电离溶质，建立了定量的结构-保留关系。在IAM. pc上用高效液相色谱法测定色谱指标logk （IAM）。DD2色谱柱为53种结构多样的化合物，包括中性、酸性和碱性化合物。与中性化合物不同，电离化合物的IAM色谱保留受其分子电荷状态的影响。当将每分子平均净电荷（δ）作为第六个变量引入修正后的LSER模型时，对于包含可电离溶质的测试集，LSER回归系数得到了显著提高。酸性和碱性化合物的δ系数差异较大，说明分子电子因子对酸性和碱性化合物在IAM柱上的滞留率有显著影响。含羧基的酸性化合物的离子化倾向于损害其在IAM上的保留，而碱性化合物的离子化则没有这种明显的影响。此外，与磷脂极性头的额外相互作用可能引起碱性化合物保留的一定变化。计算和实验保留指数的比较表明，通过添加分子电子因子修正的半经验LSER能够充分再现所研究的不同结构溶质的实验保留因子。(c) 2006 Elsevier B.V.版权所有
Linear solvation energy relationships (LSERs) amended by the introduction of a molecular electronic factor were employed to establish quantitative structure-retention relationships using immobilized artificial membrane (IAM) chromatography, in particular ionizable solutes. The chromatographic indices, log k(IAM), were determined by HPLC on an IAM.PC.DD2 column for 53 structurally diverse compounds, including neutral, acidic and basic compounds. Unlike neutral compounds, the IAM chromatographic retention of ionizable compounds was affected by their molecular charge state. When the mean net charge per molecule (delta) was introduced into the amended LSER as the sixth variable, the LSER regression coefficient was significantly improved for the test set including ionizable solutes. The delta coefficients of acidic and basic compounds were quite different indicating that the molecular electronic factor had a markedly different impact on the retention of acidic and basic compounds on IAM column. lonization of acidic compounds containing a carboxylic group tended to impair their retention on IAM, while the ionization of basic compounds did not have such a marked effect. In addition, the extra-interaction with the polar head of phospholipids might cause a certain change in the retention of basic compounds. A comparison of calculated and experimental retention indices suggested that the semi-empirical LSER amended by the addition of a molecular electronic factor was able to reproduce adequately the experimental retention factors of the structurally diverse solutes investigated. (c) 2006 Elsevier B.V. All rights reserved.