Wainer I W, Alembik M C, Smith E
J Chromatogr. 1987 Feb 6;388(1):65-74. doi: 10.1016/s0021-9673(01)94466-8.
The effect of the steric structure and concentration of the mobile phase modifier on the retention (kappa') and stereoselectivity (alpha) of a series of enantiomeric amides has been investigated. The amides were chromatographed on a commercially available cellulose tribenzoate chiral stationary phase (CSP) using mobile phases composed of hexane and two homologous series of alcohols: methanol, ethanol, 1-propanol and 2-propanol, 2-butanol, 2-pentanol, 2-hexanol. The results of the study indicate that the alcoholic mobile phase modifiers compete with the solutes for achiral and chiral binding sites and that the steric bulk around the hydroxyl moiety of the modifier plays a role in this competition. Increased steric bulk tends to result in increased kappa' and alpha. However, the results also suggest that the effect of the alcoholic mobile phase modifiers on stereoselectivity may also be due to binding to achiral sites near or at the chiral cavities of the CSP which alters the steric environment of these cavities.
研究了流动相改性剂的空间结构和浓度对一系列对映体酰胺保留值（κ'）和立体选择性（α）的影响。这些酰胺在市售的三苯甲酸纤维素手性固定相（CSP）上进行色谱分析，流动相由己烷和两个同系醇系列组成：甲醇、乙醇、1-丙醇和2-丙醇、2-丁醇、2-戊醇、2-己醇。研究结果表明，醇类流动相改性剂与溶质竞争非手性和手性结合位点，并且改性剂羟基部分周围的空间位阻在这种竞争中起作用。空间位阻增加往往会导致κ'和α增加。然而，结果还表明，醇类流动相改性剂对立体选择性的影响也可能是由于与CSP手性腔附近或处的非手性位点结合，从而改变了这些腔的空间环境。
