Ilisz István, Grecsó Nóra, Palkó Márta, Fülöp Ferenc, Lindner Wolfgang, Péter Antal
Department of Inorganic and Analytical Chemistry, University of Szeged, Dóm tér 7, H-6720 Szeged, Hungary.
Department of Inorganic and Analytical Chemistry, University of Szeged, Dóm tér 7, H-6720 Szeged, Hungary; Institute of Pharmaceutical Chemistry, University of Szeged, Eötvös u. 6, H-6720 Szeged, Hungary.
J Pharm Biomed Anal. 2014 Sep;98:130-9. doi: 10.1016/j.jpba.2014.05.012. Epub 2014 May 17.
Procedures for the direct high-performance liquid chromatographic enantiomer separation of four bicyclo[2.2.2]octane-based 3-amino-2-carboxylic acids were developed in polar-ionic mode on zwitterionic chiral stationary phases (CSPs) based on cinchonane alkaloide quinine, quinidine and chiral sulfonic acid motifs. The effects of the mobile phase composition including the type of acid and base additives, the structures of the analytes and temperature were investigated. Experiments were performed at constant mobile phase compositions in the temperature range 10-50°C in order to study the effects of temperature, and thermodynamic parameters were calculated from plots of ln k or ln α vs. 1/T. Some mechanistic aspects of the chiral recognition process are discussed with respect to the structures of the analytes. It was found that the enantiomeric separations were in most cases enthalpically driven, but entropically driven separation was also observed. The sequence of elution of the enantiomers on the pseudo-enantiomerically behaving CSPs was determined in all cases.
基于金鸡纳烷生物碱奎宁、奎尼丁和手性磺酸基序的两性离子手性固定相（CSPs），在极性离子模式下开发了四种双环[2.2.2]辛烷基3-氨基-2-羧酸的直接高效液相色谱对映体分离方法。研究了流动相组成（包括酸碱添加剂类型）、分析物结构和温度的影响。为了研究温度的影响，在10 - 50°C的温度范围内，在恒定的流动相组成下进行实验，并根据ln k或ln α对1/T的曲线计算热力学参数。针对分析物的结构，讨论了手性识别过程的一些机理方面。结果发现，在大多数情况下，对映体分离是由焓驱动的，但也观察到了由熵驱动的分离。在所有情况下，都确定了在表现出假对映体行为的CSPs上对映体的洗脱顺序。
