Department of Chemistry, Wayne State University, Rm 185 Chemistry, Detroit, MI 48202, USA.
J Chromatogr A. 2019 Apr 12;1590:130-145. doi: 10.1016/j.chroma.2019.01.028. Epub 2019 Feb 2.
The solvation parameter model is used to characterize the retention properties of poly(octylmethylsiloxane), poly(dimethyldiphenylsiloxane), silphenylene-dimethylsiloxane copolymer, poly(dimethylmethyltrifluoropropylsiloxane), poly(3-cyanopropylphenyldimethylsiloxane), and poly(ethylene glycol) (SPB-Octyl, HP-5, Rxi-17, Rxi-5Sil MS, Rtx-OPP, DB-1701, DB-225, Rtx-440 and HP-INNOWAX) stationary phases over an extended temperature range from 60 °C to close to the maximum column operating temperature. System maps constructed from the system constant database are used to evaluate the influence of temperature on the contribution of intermolecular interactions to differences in selectivity. None of the stationary phases are hydrogen-bond acids. Increasing temperature reduces the contribution from cavity formation/dispersion, dipole-type interactions and hydrogen-bond basicity in a stationary phase specific manner with their preservation to the highest temperature studied for each column. Electron lone pair interactions are generally repulsive at lower temperatures becoming attractive and leading to an increase in retention at higher temperatures.
溶剂参数模型用于描述聚（辛基甲基硅氧烷）、聚（二甲基二苯基硅氧烷）、硅菲二甲基硅氧烷共聚物、聚（二甲基甲基三氟丙基硅氧烷）、聚（3-氰丙基苯基二甲基硅氧烷）和聚（乙二醇）（SPB-辛基、HP-5、Rxi-17、Rxi-5Sil MS、Rtx-OPP、DB-1701、DB-225、Rtx-440 和 HP-INNOWAX）在较宽温度范围内（从 60°C 到接近最高柱操作温度）的保留特性。从系统常数数据库构建的系统图用于评估温度对分子间相互作用对选择性差异贡献的影响。没有一种固定相是氢键酸。随着温度的升高，固定相以特定的方式减少空腔形成/分散、偶极相互作用和氢键碱性的贡献，每种色谱柱都保留到研究的最高温度。电子孤对相互作用在较低温度下通常是排斥的，在较高温度下变得吸引，导致保留增加。
