Zhu Zexi, Zhang Guohua, Li Bao, Liu Minghua, Wu Lixin
State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, 130012, Changchun, China.
Key Laboratory of Physics and Technology for Advanced Batteries (Ministry of Education), College of Physics, Jilin University, Changchun, China.
Nat Commun. 2024 Sep 13;15(1):8033. doi: 10.1038/s41467-024-52402-6.
During the construction of supramolecular polymers of smaller nanoparticles/nanoclusters bearing hierarchy and homochirality, the mechanism understanding via intuitive visualization and precise cross-scale chirality modulation is still challenging. For this goal, a cooperative self-assembly strategy is here proposed by using ionic complexes with uniform chemical composition comprising polyanionic nanocluster cores and surrounded chiral cationic organic components as monomers for supramolecular polymerization. The single helical polymer chains bearing a core-shell structure at utmost length over 20 μm are demonstrated showing comparable flexibility resembling covalent polymers. A nucleation-elongation growth mechanism that is not dealt with in nanoparticle systems is confirmed to be accompanied by strict chiral self-sorting. A permeable membrane prepared by simple suction of such supramolecular polymers displays high enantioselectivity (e.e. 98% after four runs) for separating histidine derivatives, which discloses a benefiting helical chain structure-induced functionalization for macroscopic supramolecular materials in highly efficient racemate separation.
在构建具有层次结构和同手性的较小纳米颗粒/纳米团簇的超分子聚合物过程中，通过直观可视化和精确的跨尺度手性调制来理解其机制仍然具有挑战性。为了实现这一目标，本文提出了一种协同自组装策略，使用具有均匀化学成分的离子络合物作为超分子聚合的单体，该离子络合物由聚阴离子纳米团簇核心和周围的手性阳离子有机组分组成。实验证明，单螺旋聚合物链的最大长度超过20μm，具有核壳结构，显示出与共价聚合物相当的柔韧性。一种在纳米颗粒系统中未涉及的成核-伸长生长机制被证实伴随着严格的手性自分类。通过简单抽吸这种超分子聚合物制备的渗透膜在分离组氨酸衍生物时表现出高对映选择性（四次运行后对映体过量值为98%），这揭示了螺旋链结构诱导的功能化对宏观超分子材料在高效外消旋体分离中的益处。
