计量置换理论在多糖类手性固定相手性识别机理研究中应用.pdfVIP

中国化学会第四届全国分子手性学术研讨会暨2011 绿色手性论坛 手性分子合成与拆分 计量置换理论在多糖类手性固定相手性识别机理研究中的应用 项翠，张华，卢小太，姚碧霞，翁文* (漳州师范学院化学与环境科学系) 摘 要：考察了萘普生在二种多糖类手性固定相（Chiralpak IA 和Chiralcel OD-H ）上的拆分，探 讨了流动相中极性添加剂的种类及含量对手性拆分的影响，利用计量置换理论对色谱数据进行了拟 合，预测并验证了对映异构体的洗脱顺序随极性添加剂含量的变化而反转的现象。 关键词：萘普生；手性拆分；多糖类手性固定相；计量置换理论；洗脱顺序反转 Application of the stoichiometric displacement theory for retention in chiral recognition mechanism study with polysaccharide-based CSPs * Cui Xiang, Hua Zhang, Xiaotai Lu, Bixia Yao, Wen Weng (Department of Chemistry and Environmental Science, Zhangzhou Normal University,) Abstract ：Enantioseparation of naproxen was performed on two polysaccharide-based chiral stationary phases (CSPs), Chiralpak IA and Chiralcel OD-H. The effects of the type and the content of polar modifier in the mobile phase on the enantioseparation were investigated. The stoichiometric displacement theory for retention (SDT-R) theory was used to fit the chromatographic data. Reversal of elution order for two enantiomers of naproxen induced by the content of polar modifier was predicted based on the model and confirmed by experiment. Keywords: Naproxen; enantioseparation; polysaccharide-based csps; stoichiomeric displacement theory for retention; reversal of elution order 非甾体抗炎镇痛药萘普生，两个对映体的药效差异很大，(S)-(+)构型的药效为(R)-(−)构型的 35 倍，其对映异构体的手性分离具有重要意义。国内外关于萘普生对映体拆分机理的研究工作相对较 少。利用高效液相色谱手性固定相拆分萘普生时，萘普生作为一种溶质，流动相极性添加剂与其之 间的置换应该是计量的而且遵守计量置换保留模型(Stoichiometric displacement theory for retention, SDT-R)[1-3] ，其表达式： log k = log I − Z log [D] (1) 式中k 是萘普生的保留因子，log I 是与萘普生对HPLC 固定相的亲和势有关的常数，D 为流动相中 置换剂的浓度。若log k 对log [D]作图呈线性关系，则log I 和Z 可通过拟合直线的斜率和截距求得。 log I 可表征底物与固定相作用力的大小，Z 则表示1mol