物理化学学报 >> 2026, Vol. 42 >> Issue (10): 100256.doi: 10.1016/j.actphy.2026.100256

论文 上一篇    下一篇

非手性低聚苯胺多级手性纳米带：温度诱导的螺旋反转及对映选择性结晶应用

缪正杰1, 周传强1,2,*(), 任园园1, 徐香平1, 解菊1, 韩杰1,*()   

  1. 1 扬州大学化学与材料学院, 江苏省绿色功能材料与环境化学重点实验室, 江苏 扬州 225002
    2 扬州大学测试中心, 江苏 扬州 225002
  • 收稿日期:2025-12-13 修回日期:2026-02-05 录用日期:2026-02-09 发布日期:2026-09-03
  • 通讯作者: Email: cqzhou@yzu.edu.cn (周传强)hanjie@yzu.edu.cn (韩杰)

Hierarchical chiral nanoribbons of achiral oligoaniline: temperature induced helicity inversion and enantioselective crystallization application

Zhengjie Miao1, Chuanqiang Zhou1,2,*(), Yuanyuan Ren1, Xiangping Xu1, Ju Xie1, Jie Han1,*()   

  1. 1 Jiangsu Provincial Key Laboratory of Green & Functional Materials and Environmental Chemistry, College of Chemistry and Materials, Yangzhou University, Yangzhou 225002, Jiangsu Province, China
    2 Testing Center, Yangzhou University, Yangzhou 225002, Jiangsu Province, China
  • Received:2025-12-13 Revised:2026-02-05 Accepted:2026-02-09 Published:2026-09-03
  • Contact: Email: cqzhou@yzu.edu.cn (Chuanqiang Zhou)hanjie@yzu.edu.cn (Jie Han)

RichHTML

5

PDF

241

赞

补充材料

1

摘要：

构筑具有可调控手性的多级手性纳米结构，对发展手性光学材料与手性分离技术具有重要意义。然而，基于手性分子构筑的手性纳米结构，在实际应用中常受单体固有手性干扰问题的制约。本文报道了一种利用非手性低聚苯胺，通过简便且高效的方法合成多级手性纳米带的策略。在该非手性体系中，苯胺经氧化反应生成中间态纳米线，再通过多级自组装过程形成螺旋扭曲的纳米带。值得注意的是，仅通过调控反应温度，即可实现纳米带扭转方向及超分子手性的调控甚至反转。机理研究表明，氧化过程中会生成非手性三聚苯胺衍生物；分子间相互作用随温度发生变化，进而调控了非对称自组装过程。所制备的多级手性纳米带成功应用于外消旋氨基酸混合物的对映选择性结晶，无需引入任何外源性手性物质即可实现高效手性拆分。本研究为在非手性体系中构筑多级手性纳米结构提供了切实可行的策略，并展示了其在手性分离领域的应用潜力。

关键词: 超分子手性, 多级螺旋结构, 非手性制备, 低聚苯胺, 对映选择性结晶

Abstract:

Hierarchical chiral nanostructures with controllable chirality are highly desirable due to their novel chirality-related applications. They predominantly rely on chiral molecules; however, the intrinsic chirality interference problem for applications such as chiral separation cannot be ignored. Herein, we report the synthesis of hierarchical chiral nanoribbons from achiral oligoanilines through a facile but effective route, where the oxidation of aniline in achiral system leads to the formation helically twisted nanoribbons through a hierarchical self-assembly process involving intermediate nanowires. Remarkably, both the torsion direction and supramolecular chirality can be modulated and even reversed by simply adjusting the reaction temperature. Mechanistic investigations revealed that achiral oligoaniline of triphenylamine derivative was generated during the oxidation process, where the asymmetrical self-assembly was modulated by intermolecular interactions with temperature. The resulting hierarchical chiral nanoribbons were successfully employed to induce enantioselective crystallization of amino acids from racemic mixtures, enabling effective chiral resolution without the introduction of any extrinsic chiral species. This work presents a feasible strategy for achieving hierarchical chiral nanostructures in an achiral system and showcases its practical application in chiral separation using exclusively achiral materials.

Key words: Supramolecular chirality, Hierarchical helices, Achiral fabrication, Oligoaniline, Enantioselective crystallization