Beijing National Laboratory for Molecular Sciences CAS Key Laboratory of Colloid Interface and Chemical Thermodynamics, Institute of Chemistry, Chinese Academy of Science, Beijing, 100190, P. R. China.
Henan Provincial Key Laboratory of Surface and Interface Science, Zhengzhou University of Light Industry, Zhengzhou, Henan, 450002, P. R. China.
Small. 2016 Sep;12(34):4743-52. doi: 10.1002/smll.201600842. Epub 2016 Jun 1.
Controlled hierarchical self-assembly of synthetic molecules into chiral nanoarchitectures to mimic those biological chiral structures is of great importance. Here, a low-molecular-weight organogelator containing a benzimidazole moiety conjugated with an amphiphilic l-glutamic amide has been designed and its self-assembly into various hierarchical chiral nanostructures is investigated. Upon gel formation in organic solvents, 1D chiral nanostructure such as nanofiber and nanotube are obtained depending on the solvents. In the presence of transition and rare earth metal ions, hierarchical chiral nanostructures are formed. Specifically, the addition of TbCl3 , EuCl3 , and AgNO3 leads to nanofiber structures, while the addition of Cu(NO3 )2 , Tb(NO3 )3 , or Eu(NO3 )3 provides the microflower structures and microtubular flower structures, respectively. While Eu(III) and Tb(III)-containing microtubular flowers keep the chirality, the Cu(II)-coordinated microflowers lose chirality. More interestingly, the nanofibers formed by the gelator coordinated with Eu(III) or Tb(III) ions show not only the supramolecular chirality but also the circularly polarized luminescence.
控制合成分子的层次自组装成手性纳米结构，以模拟那些生物手性结构，这是非常重要的。在这里，设计了一种含有苯并咪唑部分与两亲性 l-谷氨酸酰胺连接的低分子量有机凝胶剂，并研究了其自组装成各种层次手性纳米结构。在有机溶剂中形成凝胶时，根据溶剂的不同，可以得到 1D 手性纳米结构，如纳米纤维和纳米管。在过渡金属和稀土金属离子的存在下，形成了层次手性纳米结构。具体而言，添加 TbCl3、EuCl3 和 AgNO3 导致形成纳米纤维结构，而添加 Cu(NO3)2、Tb(NO3)3 或 Eu(NO3)3 分别提供微花结构和微管状花结构。虽然含有 Eu(III)和 Tb(III)的微管状花保持手性，但 Cu(II)配位的微花失去手性。更有趣的是，由与 Eu(III)或 Tb(III)离子配位的凝胶剂形成的纳米纤维不仅表现出超分子手性，而且还表现出圆偏振发光。
