研究了HPLC法羟丙基-β-环糊精(HP-β-CD)手性流动相添加剂对萘普生对映体的保留机制,建立了保留因子与[CD]、[H^+]、包结常数以及萘普生的解离常数的关系式,并结合实验对此关系式进行了验证,结果表明此关系式对手性添加剂、pH等因素对拆分的影响具有一定的理论指导.保留因子(k)的倒数1/k对HP-β-CD的浓度呈良好的线性关系,证明HP-β-CD与萘普生对映体形成的包合比是1/1包合物.计算了手性分离过程中的热力学参数,结果表明HP-β-CD对萘普生对映体的分离过程主要是一个焓驱动的过程,包合过程是一个放热过程.通过比较手性选择体结构,探讨了HP-β-CD拆分萘普生对映体的机理,进一步分析表明HP-β-CD能拆分萘普生对映体的主要因素是尺寸大小相匹配、构象诱导作用和偶极-偶极作用.
Enantiomers of naproxen with added hydroxypropyl-β- cyclodextrin ( HP- β- CD) in high performance liquid chromatographic (HPLC) mobile phase on the retention had been investigated. Relationship equations of capacity factor with [CD] ,[H^+ ] and inclusion complex and dissociation constants of naproxen were built and demonstrated by experiments, results showed that the relationship equation can forecast on separation process. Graph of Ilk vs [ HP-β-CD] gave good linear relationship, indicating the stoichiometric ratio of 1/1. On the other hand, the thermodynamic parameters of inclusion complexes were determined, it was demonstrated that separation of naproxen enantiomers was enthalpy-driven process, and the process of inclusion was exothermic. In addition, separation mechanism on naproxen enantiomers with HP-β-CD as a mobile phase modifier was discussed by comparing the structure of cyclodextrins. The primary factors that HP-β-CD can separate naproxen enantiomers are the size-size matches, the conformation induction and the dipole-dipole interaction.