量化计算辅助解析杯[4]芳烃固定相对萘胺和苯二胺的保留机制  

Assisted elucidation for retention mechanism of naphthylamine and benzenediamine on calix[4]arene stationary phase by quantum chemistry calculation method

作　　者：胡锴[1] 徐占辉 张军强[1] 解静[1] 闻付勇[1] 冶保献[1] 吴养洁[1] 张书胜[1] 

机构地区：[1]郑州大学化学系,河南省化学生物与有机化学重点实验室,郑州450052

出　　处：《中国科学（B辑）》2009年第8期857-862,共6页Science in China(Series B)

基　　金：国家自然科学基金(批准号:20875083,20775073);环境化学与生态毒理学国家重点实验室开放课题(批准号:KF2008-22)资助

摘　　要：杯芳烃对客体具有优异的识别作用,可作为液相色谱的固定相.本文以萘胺(NA)、苯二胺(BDA)位置异构体为溶质探针,考察其在杯[4]芳烃(Cx4)固定相上的色谱分离,用量子化学计算辅助研究了其在Cx4芳烃固定相上的保留机制.结果表明,用DFT-B3LYP/STO-3G**量化计算方法,获得了质子化溶质与Cx4形成的Cx4-HBDA+、Cx4-HNA+超分子结构,直观地观察到了HBDA+、HNA+与Cx4的作用主要是π-π疏水作用和氢键作用.超分子Cx4-HBDA+和Cx4-HNA+的ΔG数值、稳定性与其色谱保留行为一致.Calixarenes possess the outstanding recognition property for the guest compounds. They have been extensively used as stationary phases. In the present work, aromatic naphthylamine （NA） and benzenediamine （BDA） po- sitional isomers were selected as the probe, their retention mechanism on the calix[4]arene （Cx4） stationary phase were investigated with the assistance of quantum chemistry calculation （QCC） method. The optimized supramolecu- lar structures of Cx4-HBDA＋ and Cx4-HNA＋ were obtained with the software DFT-B3LYP and STO-3G＊＊ basis set. The structures showed that there exist different hydrogen bonding and π-π interactions between aromatic amines and Cx4. The thermodynamic Gibbs free energy changes （AG） of Cx4-HBDA＋ and Cx4-HNA＋ formation were also obtained by frequency calculation with DFT-B3LYP/STO-3G＊＊. The AG values and supramolecular stability were consistent with the retention behaviors of aromatic amines on Cx4 stationary phases.

关 键 词：芳烃固定相 萘胺 苯二胺 保留机制 量化计算 

分 类 号：O657.7[理学—分析化学]