摘要
手性作为自然界中的普遍现象,显著影响物质性能.手性物质的精准构筑和对映体识别技术有望对医药、信息、材料电脑等领域提供核心支持,但仍面临巨大挑战.以双酚A为原料,成功合成了高手性纯的(R)-3,3,3',3'-四甲基-1,1'-螺二茚-7,7'-二醇((R)-6,6'-TMSOL),通过与靛红分子间傅克反应,制备出手性自具微孔聚合物((R)-HSBI-Is),并通过核磁共振、红外光谱、紫外光谱、比表面积及孔径分析、热重分析等手段进行了全面表征与分析.研究结果显示,该聚合物具有高比表面积和强的荧光发光,对L-苯丙氨酸具有选择性的显著荧光增强效果,L和D构型选择性达34.9,可作为L-苯丙氨酸的特异性手性识别剂.
Abstract
Chirality,a ubiquitous phenomenon in nature,profoundly influences material properties.The precise synthesis of chiral compounds and enantiomer recognition techniques hold promise as pivotal advancements in the realms of medicine,informatics,and materials science,yet remain a formidable challenge.In this paper,we prepared a monochiral self-forming microporous polymers((R)-HSBI-Is)through direct-synthesis method,and applied it for chiral recognition of phenylalanine.First,commencing with bisphenol A,racematic 3,3,3',3'-tetramethyl-1,1'-spirodine-7,7'-diol(6,6'-TMSOL)was synthesized,and form transitional complex derivates through adding chiral reagents(L-menthyl chloroformate).After three times recrys-tallization under-18 ℃,the diastereoisomers of the complex derivates were successfully separated due to their different solubility.After hydrolysis reaction,the auxiliary groups were removed and chiral monomer was synthesized.This study achieved the artful synthesis of pure(R)-3,3,3',3'-tetramethyl-1,1'-spirodine-7,7'-diol((R)-6,6'-TMSOL).Subsequently,chiral polymer of intrinsic microporosity((R)-HSBI-Is)were crafted through Friedel-Crafts reaction with isatin molecules.And we delved the mechanism of synthesizing chiral polymers.These polymers were comprehensively evaluated using techniques such as nuclear magnetic resonance,infrared spectroscopy,UV spectroscopy,specific surface area and pore size analysis,and thermogravimetric analysis.Our findings reveal that the polymer boasts a high specific surface area and robust fluorescence.It also shows a great performance in thermal stability.The fluorescence experiments on chiral molecules(phenylalanine,tryptophan,1,1'-binaphthyl-2,2'-diol(BINOL),1,1'-spirobiindane(SPINOL)and 1-phenylethanol)were carried out to testify the recognition performance of chiral polymer.The results proved that the polymer exhibits a remarkable selective fluores-cence enhancement towards L-phenylalanine.Specifically,the L-and D-configuration selectivity achieved is 34.9,position-ing it as an exceptional chiral recognition agent for L-phenylalanine.
基金项目
国家自然科学基金(22078174)
教育部产学合作协同育人项目(231106429150016)
江苏省创新能力建设计划——江苏省技术创新中心课题(KF2024004)
维普
万方数据