新型靛红衍生化β-环糊精键合SBA-15液相色谱固定相的制备与表征  

Preparation and Characterization of a Novel Isatin Derivative of β-Cyclodextrin-bonded SBA-15 Stationary Phase for HPLC

作　　者：张杨[1] 李来生[1] 程彪平[1] 周仁丹[1] 聂桂珍[1] 

机构地区：[1]南昌大学分析测试中心,南昌330047

出　　处：《分析化学》2014年第3期375-383,共9页Chinese Journal of Analytical Chemistry

基　　金：国家自然科学基金(No.21165012);江西省自然科学基金(No.2010GZH0089);江西省教育厅科技项目(No.GJJ11274)资助~~

摘　　要：利用靛红的羰基与β-环糊精单取代乙二胺的缩合反应,合成得到种靛红衍生化β-环糊精Schiff碱类化合物。以3-异氰酸丙基三乙氧基硅烷为偶联剂,将其键合到自制的有序介孔二氧化硅材料SBA-15表面,制得种新型的靛红衍生化β-环糊精键合SBA-15液相色谱固定相(ISCDP)。分别对β-环糊精衍生物、SBA-15及固定相进行必要的结构表征。在反相色谱条件下,以卤代尿嘧啶类极性化合物和二取代苯位置异构体为探针,评价新固定相的基本色谱性能。在极性有机溶剂和反相模式下,将新固定相分别用于β-受体阻滞剂药物和丹磺酰化氨基酸对映体的拆分,探讨了相关色谱分离机理。实验表明,靛红吲哚环的引入,增强了环糊精类固定相对卤代尿嘧啶的反相色谱分离能力,分析时间小于7 min。固定相分离硝基苯胺、氨基苯酚和苯二酚的位置异构体时也表现出较高的立体选择性,其中对位异构体均后被洗脱,这与包结作用相关;靛红衍生化β-环糊精配体也提高了固定相的手性分离能力,除疏水作用外,靛红衍生化β-环糊精配体还能提供偶极、氢键、π-π和包结等作用,多种协同作用力有利于提高新固定相的手性和非手性分离的选择性。SBA-15作为键合基质,其有序的孔结构有利于保持色谱柱的良好渗透性和小的传质阻力,在快速高效分离分析中具有应用潜能。An isatin derivative of β-cyclodextrin Schiff base was first synthesized by the condensation reaction between the carbonyl group of isatin and ethylenediamino group of the mono-substituted β-cyclodextrin. The Schiff base ligand was chemically linked to homemade ordered mesoporous SBA-15 silica gel via 3-（triethoxysilyl）propyl isocyanate coupling agent. In this way, a novel isatin derivative of β-eyclodextrin- bonded SBA-15 stationary phase （ISCDP） was prepared for HPLC. Its chemical and physical parameters were characterized by infrared spectroscopy, mass spectroscopy, elemental analysis, thermogravimetric analysis, scanning electron microscopy, transmission electron microscopy, X-ray diffraction and BET specific surface area analysis. The basic chromatographic property of ISCDP was evaluated by using polar halogenated uracils and disubstituted benzene positional isomers as solute probes in reversed-phase chromatography. ISCDP was also used to enantioseparate two β-blocker drugs in polar organic mode and two dansyl amino acids in reversed- phase mode, respectively. The related chromatographic separation mechanism was also discussed. Above studies were expected to provide experimental basis for the practical application of ISCDP in the future. The results showed that the introduction of isatin indole ring could enhanced the reversed-phase chromatographic separation ability of ISCDP for halogenated uracils within 7 min. The new packing also exhibited high stereoselectivity for the position isomers of nitroaniline, aminophenol and benzenediol, in which the para isomers were finally eluted due to strong inclusion interaction between the isatin derivative of β-cyclodextrin ligand and the isomers. Meanwhile, the introduction of isatin indole ring could also improve the ehiral separation ability of ISCDP. For example the fast enantioseparations of chiral β-adrenergic blockers and dansyl-amino acids on ISCDP were achieved within 20 min （Rs 〉 1.3 ）. Obviously, besides hydrophobicity, various synergisti

关 键 词：高效液相色谱法 靛红衍生化β-环糊精键合相 SBA-15 手性和非手性分离机理 

分 类 号：O657.72[理学—分析化学]