Al-Haj M A, Haber P, Kaliszan R, Buszewski B, Jezierska M, Chilmonzyk Z
Department of Biopharmaceutics and Pharmacodynamics, Medical University of Gdańsk, Poland.
J Pharm Biomed Anal. 1998 Dec;18(4-5):721-8. doi: 10.1016/s0731-7085(98)00287-8.
The retention characteristics of a newly synthesized stationary phase were determined for reversed-phase high-performance liquid chromatography obtained by chemical immobilization of cholesterol on spherical silica gel. For a designed series of analytes the retention factors, log k, were determined at several compositions of the methanol-water mobile phase. Logarithms of retention factor corresponding to a hypothetical pure water eluent, log k(w), were calculated by extrapolation of the linear relationships of individual log k data versus volume percent of methanol. The series of 24 test analytes were characterized structurally by means of the logarithms of n-octanol-water partition coefficients, log P, by a set of the linear solvation energy relationship (LSER)-based descriptors of the polarity and bulkiness of the analytes and by structural descriptors of analyte size and polarity acquired by molecular modelling. Quantitative structure retention relationships (QSRR) were derived by multiple regression analysis using the three groups of structural descriptors of analytes and the log k(w) data determined on the new stationary phase. For the sake of comparison the corresponding QSRR equations were also derived for retention parameters determined on a standard octadecylsilica and on the so-called immobilized artificial membrane (IAM) stationary phase. The QSRR analysis clearly proved distinctive retention properties of the new cholesterol-silica stationary phase. It has been concluded that the new phase may possess valuable analytical specificity. Its application for modelling penetration of xenobiotics through biological membranes appears rather unlikely.
通过将胆固醇化学固定在球形硅胶上获得的反相高效液相色谱法，测定了一种新合成固定相的保留特性。对于一系列设计好的分析物，在甲醇 - 水流动相的几种组成下测定了保留因子log k。通过将各个log k数据与甲醇体积百分比的线性关系进行外推，计算出对应于假设纯水洗脱液的保留因子对数log k(w)。通过正辛醇 - 水分配系数的对数log P、基于线性溶剂化能关系（LSER）的一组分析物极性和体积描述符以及通过分子建模获得的分析物大小和极性的结构描述符，对24种测试分析物系列进行了结构表征。使用分析物的三组结构描述符和在新固定相上测定的log k(w)数据，通过多元回归分析得出定量结构保留关系（QSRR）。为了进行比较，还针对在标准十八烷基硅胶和所谓的固定化人工膜（IAM）固定相上测定的保留参数得出了相应的QSRR方程。QSRR分析清楚地证明了新的胆固醇 - 硅胶固定相具有独特的保留特性。得出的结论是，新相可能具有有价值的分析特异性。它用于模拟异生素通过生物膜的渗透似乎不太可能。
