邻苯二甲酸酯类分子印迹聚合物预组装体系的分子模拟计算

Computational strategies for the design and study of phthalate esters-imprinted prepolymerization mixtures

以邻苯二甲酸二异癸酯(T1)及2个衍生分子T2、T3为模板分子,以α-甲基丙烯酸(MAA)、丙烯酰胺(AM)和3-氨丙基三乙氧基硅烷(APTES)为功能单体,三氯甲烷、甲醇、乙醇及乙腈为致孔剂,运用量子化学方法模拟模板分子与不同功能单体的分子印迹聚合物预组装体系的构型、能量及复合反应的结合能ΔE,以及单体与模板分子在不同溶剂中的溶剂化能。结果表明,APTES与T3以1:1摩尔比结合时形成更为稳定的复合物,最大结合能达到103.6 KJ·mol^(-1);模板分子和功能单体在三氯甲烷中的溶剂化能最小,因此三氯甲烷更适合作为溶剂。通过模拟计算,有助于揭示分子印迹聚合物识别原理,为邻苯二甲酸二异癸酯类的分子印迹聚合物制备提供理论参考。

In this study, quantum chemical method was applied for screening functional monomers and solvent in the rational design of molecularly imprinted polymer （MIP）. The B97D3/6-3 1＋g＊ method was used to investigate the geometry optimization, active sites, natural bond orbital charges, binding energies of the imprinted molecule. The theoretical results show that di-iso-decylphthalate derivant （T3） interacts with 3-aminopropyltriethoxysilane （APTES） functional monomers by hydrogen bonds, and the compound of the ratio of T3-APTES （1：1, mol：mol） had the highest stability （103.6 KJ/mol）. Moreover, the solvation energy of template molecule, and functional monomers in the chloroform were the lower than that in methanol, ethanol and acetonitrile. Computer simulations and molecular modeling can help us understand binding phenomena in MIPs on the molecular level and thus provide a route to more efficient MIP design strategies.