摘要
葫芦脲(CB[n],n为最小重复单元数)是一类由苷脲与甲醛经缩合环化而形成的大环分子,因具有良好的分子识别性能及配位性能,在分离、催化、医药、互锁分子及超分子体系构建等领域有着广泛的应用。本课题组在苷脲分子中间的桥上增加一个碳原子,得到苷脲类似物丙基二脲(TD),TD进一步与甲醛缩合环化得到一系列向日葵状葫芦脲类似物(TD[n])。与传统苷脲相比,TD容易在碳原子上衍生化,衍生物对成环反应的影响较小,容易获得TD[n]。相比CB[n]的n最小值为5,TD[n]的n最小值减小到4,TD[4]是目前为止文献报道的葫芦脲家族的最小成员。此外,这些TD[n]有的对金属离子具有很好的选择配位能力,有的对质子化有机胺具有强的外结合性能,它们分别构建了一系列一维、二维或刺激响应型超分子聚合物。研究结果为TD[n]在超分子化学等领域的进一步应用打下坚实的基础。
Cucurbiturils are a series of pumpkin-shaped macrocyles obtained from an acid-catalyzed condensation reaction of glycoluril and formaldehyde.They can bind with gases,small molecules and positive charged guests,and have been widely used in the fields of separation,catalysis,pharmaceutical,interlocked molecules,and supramolecular architectures etc.Recently,our group has synthesized a new class of Helianthus-like cucurbituril analogues (TD[n],n is the number of the repeated units) using the condensation of glycoluril-like propanediurea (2,4,6,8-tetraazabicyclo[3.3.1]nonane-3,7-dione,TD) or its derivatives with formaldehyde.Compared with glycoluril,substituents can be introduced more easily on the central methylene position of TD and the corresponding derivatives have less influence upon the cucurbituril-forming cyclization.It should be noted that the value of n in cucurbituril family is reduced to 4 for the first time and TD[4] is of smaller cavity than ever.Moreover,some TD[n]s bind selectively to metal ions,and some bind strongly with protonated amines in portal binding mode,and a series of TD[n]-based supramolecular polymers have consequently been set up,which would lay a solid foundation for their future applications in areas such as supramolecular chemistry.
作者
王巧纯
WANG Qiaochun(Key Laboratory for Advanced Materials and Institute of Fine Chemicals,School of Chemistry and Molecular Engineering,East China University of Science and Technology,Shanghai 200237,China)
出处
《功能高分子学报》
CAS
CSCD
北大核心
2019年第1期9-12,共4页
Journal of Functional Polymers
基金
国家自然科学基金(21572063)
关键词
葫芦脲
大环分子
自组装
超分子聚合物
cucurbiturils
macrocycles
self-assembly
supramolecular polymers
