A Chiral Recognition System Orchestrated by Self‐Assembly: Molecular Chirality, Self‐Assembly Morphology, and Fluorescence Response

Abstract

The newly developed oligophenylenevinylene (OPV)-based fluorescent (FL) chiral chemosensor (OPV-Me) for the representative enantiomeric guest, 1,2-cyclohexanedicarboxylic acid (1,2-CHDA: RR- and SS-form) showed the high chiral discrimination ability, resulting in the different aggregation modes of OPV-Me self-assembly: RR-CHDA directed the fibrous supramolecular aggregate, whereas SS-CHDA directed the finite aggregate. The consequent FL intensity toward RR-CHDA was up to 30 times larger than that toward SS-CHDA. Accordingly, highly enantioselective recognition was achieved. Application to the chirality sensing was also possible: OPV-Me exhibited a linear relationship between the FL intensity and the enantiomeric excess through the morphological development of stereocomplex aggregates. These results clearly show that the chiral recognition ability is manifested by the amplification cascade of the chirality difference through self-assembly.

Supramolecular chirality: a caveat in assigning the handedness of chiral aggregates

“…1 Most of the initial research activities in the field were focused on molecular chirality with a significant impact on drug design. With the advent of supramolecular chemistry, the research activity in the area boosted, extending to macroscopic chirality and opening up promising applications in drug delivery, 2 catalysis, 3 nonlinear optics, 4 chiral sensing, 5 etc. The emergence of optical properties in supramolecular assemblies is governed by excitonic interactions.…”

Fabrication and Applications of Supramolecular Chiral Assemblies

“…在生物体高度手性化的环境中, 对映体的手性识别 过程在生命活动中发挥着不可或缺的作用, 具有重要的 理论和实际研究意义, 对该过程进行模拟一直以来都是 化学家努力的方向 [84] [85] Figure 29 Chemical structure of 52 and response of vesicles self-assembled from 52 to D/L-tartrate monitored by DLS [85] 图 30 53 的组装体结构模型及其对 R/S-TBSA 的响应 [86] Figure 30 Structure model of assemblies 53 and its responses to R/S-TBSA [86] Shinkai 等 [87] [87] Figure 31 Chemical structure of 54 and fluorescent change of assembled 54 in the presence of RR/SS-CHDA [87] 聚合物的超分子手性组装体同样能应用于手性识 别领域中. 利用聚苯乙烯-聚丙烯酸嵌段共聚物 55 与 R-1,1'-联萘衍生物 R-56 的共组装, 朱亮亮等 [88] 制备了一 种超分子手性凝胶.…”

Supramolecular Chiral Discrimination of D-Phenylalanine Amino Acid Based on a Perylene Bisimide Derivative

“…The approach that was used in the present work can be considered as the initial point to use chiral perylene bisimide (PBI) based systems for the detection of specific chiral form. The supramolecular chiral discrimination of a single enantiomer over the other is reported even for other systems (Cooper et al, 2017;Gangopadhyay et al, 2017;Noguchi et al, 2017). We present here the symmetric PBI with D-phenylalanine in the amide position which acts as a chiral sensor only for the D form of the phenylalanine.…”