介孔二氧化硅对映选择性吸附的手性印迹调控  

Tunable Enantioselective Adsorption of the As⁃synthesized Mesoporous Silica Through Chiral Imprinting

作　　者：宋文尧 周张浪 杨鑫莉 陈岚[1,2] 葛广路[1,2] SONG Wenyao;ZHOU Zhanglang;YANG Xinli;CHEN Lan;GE Guanglu(CAS Key Laboratory of Standardization and Measurement for Nanoscience,National Center for Nanoscience and Technology,Beijing 100190,China;CAS Center for Excellence in Nanoscience,Beijing 100190,China;Sino-Danish College,University of Chinese Academy of Sciences,Beijing 100049,China;University of Chinese Academy of Sciences,Beijing 100049,China)

机构地区：[1]国家纳米科学中心,中国科学院纳米标准与检测重点实验室,北京100190 [2]中国科学院纳米科学卓越中心,北京100190 [3]中国科学院大学中丹学院,北京100049 [4]中国科学院大学,北京100049

出　　处：《高等学校化学学报》2021年第10期3144-3150,共7页Chemical Journal of Chinese Universities

基　　金：国家重点研发计划项目(批准号:2016YFA0200904)资助.

摘　　要：使用手性阴离子表面活性剂作为超分子模板,采用共结构导向法制备手性介孔二氧化硅(CMS),并运用圆二色谱(CD)对CMS对映选择性吸附结果进行检测,比较了有无共结构导向剂(CSDA)在介孔表面的排列对吸附选择性的影响.结果表明,当使用构型相反的手性超分子模板剂对原合成CMS材料的介孔内表面进行修饰时,可诱导结构共导向剂N‐三甲氧基硅基丙基‐N,N,N‐三甲基氯化铵(TMAPS)发生手性相反的排列进而导致完全相反的对映选择性吸附.实验证明此方法合成的CMS的对映选择性吸附及分离能力主要是由修饰在介孔表面的TMAPS螺旋排列形成的手性印迹所导致.此手性超分子模板诱导TMAPS手性印迹的策略具有一定的普适性,可对原合成介孔材料对映选择性吸附进行原位调控,对于拓展其在立体选择性识别、不对称催化及药物输送等方面的应用具有一定的指导意义.Chiral mesoporous silica(CMS)has unique chiral structure and good enantioselective adsorption properties,which can be used for the separation of racemic mixtures.The preparation and applications of the CMS have received many attentions in recent years,while less research has been conducted on the origin for the chiral selective adsorption of the CMS.In this work,CMS was prepared using chiral anionic surfactants as supramolecular templates assisted by co‐structure directing method.The enantioselective adsorption of racemic molecules and chirality for the CMS were measured using circular dichroism(CD),and the effect of mesopo‐rous surface modification with or without co‐structure directing agent TMAPS(N‐trimethoxysilylpropyl‐N,N,N‐trimethylammonium chloride)on the adsorption selectivity was compared.As a result,the as‐synthesized CMS whose inner surface is grafted with TMAPS induced by supramolecular templates with opposite chirality can produce chiral imprinting with opposite helical arrangement and thus result in opposite adsorption selecti‐vity.It has been confirmed that the enantioselective adsorption of the CMS for separating racemic mixtures is mainly caused by the chiral imprinting of TMAPS with helical arrangement grafted on the mesoporous surface.The chiral supramolecular templated TMAPS alignment to produce chiral imprinting is practical for some appli‐cations,which can in situ tune the enantioselective adsorption and separation property for the as‐synthesized mesoporous materials.This work is thought to widen the applications of the CMS in many areas such as stere‐oselective recognition,asymmetric catalysis and drug delivery etc.

关 键 词：手性介孔二氧化硅 手性超分子模板 对映选择性吸附 手性印迹 共结构导向剂 

分 类 号：O647.3[理学—物理化学] O658.9[理学—化学]