摘要
目的:采用原位热引发聚合法制备分子印迹整体柱,在高效液相色谱上考察印迹整体柱在不同色谱条件下分子印迹整体柱选择性的变化。利用计量置换模型对实验数据进行模拟,研究决定分子印迹整体柱选择性识别能力的主要因素。方法:以甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,甲苯和异辛烷为致孔剂,偶氮二异丁腈为引发剂,选择原位热引发聚合法,制备以对-羟基苯甲酸为模板的分子印迹整体柱。在高效液相色谱上考察印迹整体柱对模板分子的特异选择性;系统考察了向流动相中依次加入水、甲醇、乙醇和异丙醇4种强氢键竞争溶剂后对-羟基苯甲酸、邻-羟基苯甲酸和对-硝基苯甲酸容量因子的变化,利用计量置换模型对实验数据进行模拟。结果:制得的分子印迹整体柱对模板分子具有特异选择性;在流动相中加入强氢键竞争溶剂后,各种样品的容量因子以及印迹整体柱的选择性均降低;计量置换模型模拟结果显示lnk值用来表示分子印迹聚合物的分离效率,n值用来表示当溶质和印迹聚合物间的相互作用是氢键时,被分离样品和印迹聚合物之间相互作用的空间效应。结论:当强氢键竞争性溶剂加入流动相中时印迹聚合物孔穴结构的匹配性决定了印迹体系的特异识别能力。
OBJECTIVE In-situ thermo-initiated polymerization technique is introduced to prepare MIP monolith for HPLC,to study mechanism of molecular recognition of imprinted monolith,investigate effects of various chromatographic conditions on selectivity of MIP monolith systematically,and analyze interaction of template molecule and stationary phase or mobile phase with stoichiometric displacement model for retention.METHODS With methyl acrylic acid as functional monomer,ethylene glycol dimethacrylate as cross linker,toluene-isooctane as porogenic solvent,2,2-azobis（isobutryronitride）as initiator,imprinted monolith was synthesized by an in-situ thermo-initiated polymerization method in presence of a model imprinting molecule,p-hydroxybenzoic acid.Special selectivity of imprinted monolith in HPLC and effects of various chromatographic conditions on selectivity of MIP monolith were investigated,including different contents of water,methanol,alcohol and isopropanol in mobile phase,respectively.Achieved data were simulated through stoichiometric displacement model for retention.RESULTS Prepared monolithic MIP could offer selective recognition towards template.Retention factors of samples and selectivity of MIP monolith reduced when strong hydrogen-bonding competitive solvent was added into mobile phase.Simulation results showed that values of lnkin proposed SDM-R could be employed to characterize efficiency of MIP＇s total separation,and value of ncould be used to denote space effect of sample interacting with MIP when interaction between solutes and MIP was a hydrogen-bonding interaction.CONCLUSION Suitability of MIP cavity structure mainly determines recognizing ability of imprinting system,when a strong hydrogen-bond competitive solvent is added into mobile phase.
出处
《中国医院药学杂志》
CAS
CSCD
北大核心
2016年第15期1260-1264,共5页
Chinese Journal of Hospital Pharmacy
关键词
分子印迹聚合物
整体柱
高效液相色谱
计量置换保留模型
对-羟基苯甲酸
molecularly imprinted polymer（MIP）
monolithic column
high performance liquid chromatography（HPLC）
stoichiometric displacement model for retention（SDM-R）
p-hydroxybenzoic acid
