Beijing National Laboratory for Molecular Science (BNLMS), CAS Key Laboratory of Colloid, Interface and Chemical Thermodynamics, Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190, China.
University of Chinese Academy of Sciences , Beijing 100049, China.
ACS Appl Mater Interfaces. 2017 Oct 25;9(42):37386-37394. doi: 10.1021/acsami.7b10353. Epub 2017 Oct 12.
An l-glutamic acid terminated amphiphilic diacetylene was designed and found to self-assemble into vesicles in water and supramolecular gel with helical structures in mixed methanol/water solvent. Both the vesicles and the helices underwent topochemical photopolymerization under UV irradiation and changed to a blue color. During the self-assembly and photopolymerization, the chirality of localized l-glutamic acid was successfully transferred to polydiacetylene (PDA), which resulted in obvious CD signals in the PDA blue phase. Interestingly, the CD signals for PDA vesicles and helices were opposite due to the different packing modes in the PDA skeleton. However, although these two assembly systems own opposite supramolecular chirality, both of them showed the same enantioselective recognition of sulfinamide enantiomers, in which the assemblies with S-enantiomer turned red while the other remained blue in the presence of the R-enantiomer. It is suggested that the chiral interface composed of l-glutamic acid played an important role in the enantioselective recognition. This work revealed the function of molecular and supramolecular chirality in the supramolecular self-assembly system.
一种以 l-谷氨酸为端基的两亲性二炔被设计出来，并被发现可以在水中自组装成囊泡，在甲醇/水混合溶剂中可以组装成具有螺旋结构的超分子凝胶。囊泡和螺旋都可以在紫外光照射下进行拓扑化学反应聚合，变成蓝色。在自组装和光聚合过程中，局部 l-谷氨酸的手性成功地转移到聚二炔（PDA）中，导致 PDA 蓝相中有明显的 CD 信号。有趣的是，由于 PDA 骨架中的不同堆积方式，PDA 囊泡和螺旋的 CD 信号相反。然而，尽管这两个组装体系具有相反的超分子手性，但它们都表现出对亚砜酰胺对映体的相同对映选择性识别，其中含有 S-对映体的组装体在存在 R-对映体时变成红色，而另一个则保持蓝色。这表明由 l-谷氨酸组成的手性界面在对映体选择性识别中起着重要作用。这项工作揭示了分子和超分子手性在超分子自组装体系中的作用。
