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

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．

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

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 calix4]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.