异丁酰化L-缬氨酸功能化环糊精手性分离材料的制备和性能评价  

Preparation and Evaluation of Isobutyrylated L-Valine Functionalized Cyclodextrin Chromatographic Materials

作　　者：胡思雨 王雨楠 徐佳碧 李媛 马骁飞[1] 王勇[1] 肖殷[2] HU Si-Yu;WANG Yu-Nan;XU Jia-Bi;LI Yuan;MA Xiao-Fei;WANG Yong;XIAO Yin(School of Science,Tianjin University,Tianjin 300350,China;School of Chemical Engineering and Technology,Tianjin University,Tianjin 300350,China)

机构地区：[1]天津大学理学院,天津300350 [2]天津大学化工学院,天津300350

出　　处：《分析化学》2023年第11期1756-1773,共18页Chinese Journal of Analytical Chemistry

基　　金：国家重点研发计划项目(No.2019YFC1905500);国家自然科学基金项目(Nos.21922409,22274109,21976131)资助

摘　　要：环糊精(CD)亲水羟基的精准功能化是提升其手性识别能力的重要途径。本研究在CD骨架中引入异丁酰化L-缬氨酸功能团,并利用“巯基-烯”点击化学反应合成了一种具有全新结构的CD手性分离材料。通过固体核磁共振(^(13)C-NMR)和红外光谱(FTIR)表征了其结构,元素分析结果计算表明,CD表面负载量为0.53μmol/m^(2)。采用高效液相色谱(HPLC)反相模式证实了此材料对黄烷酮和异噁唑啉两大类手性对映体具有优异的手性拆分性能。实验结果表明,黄烷酮类分子中的苯并吡喃酮结构存在取代基团,会降低分析物的保留能力并影响拆分效果,而对苯环进行取代则能有效提升拆分性能;同时,改性后的CD有利于对含有两个苯基基团的异噁唑啉类样品的手性拆分。此外,异丁酰化L-缬氨酸对CD的修饰使CD具备了完全分离二甲苯异构体的能力,证实了此类材料在解决同分异构体分离难题中的巨大潜力。Precise functionalization of hydrophilic hydroxyl group of cyclodextrin(CD)is an essential way to improve its chiral recognition ability.In this study,an isobutylated L-valine functional group was introduced into the cyclodextrin framework,and a new CD chiral separation material was synthesized by means of“Thiol-ene”click chemical reaction.The structure was characterized by solid state nuclear magnetic resonance spectroscopy(^(13)C-NMR)and Fourier transform infrared spectroscopy(FTIR).Elemental analysis results showed that the surface loading of CD was 0.53μmol/m^(2).The excellent chiral resolution performance of the new material for two major chiral enantiomers,flavanones and isoxazolines,was confirmed by high performance liquid chromatography(HPLC)in reversed-phase mode.The results showed that the substitution of benzopyranone on flavanones could weaken the retention ability and resolution effect of the analytes,while the substitution of benzene ring could effectively improve the resolution performance.Meanwhile,the modified CD was favorable for the chiral resolution of isoxazolines samples which contained two phenyl groups.In addition,it was found that the functionalized CD was able to completely separate xylene isomers for the first time through the regulation for the CD cavity by isobutylated L-valine,demonstrating the great potential of this material in solving difficult issue of isomer separation.

关 键 词：环糊精 高效液相色谱 手性识别 点击化学 

分 类 号：TB34[一般工业技术—材料科学与工程] O636.12[理学—高分子化学]