Key Laboratory of Colloid and Interface Chemistry, Ministry of Education and School of Chemistry and Chemical Engineering , Shandong University , Jinan 250100 , People's Republic of China.
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences , Nanyang Technological University , 21 Nanyang Link , Singapore 637371 , Singapore.
J Am Chem Soc. 2019 Jun 26;141(25):9946-9954. doi: 10.1021/jacs.9b03502. Epub 2019 Jun 14.
Developing artificial systems to mimic the emergence of chirality is of vital importance in better understanding the mysterious origin of natural homochirality and guiding the design of advanced chiroptical materials. Herein, we present a DNA-inspired control over the emergence of supramolecular nanoscale chirality in multiple hydrogen-bonded self-assemblies. N-Terminated aromatic amino acids bearing serine and aromatic domains could self-assemble into lamellar microsheets without nanoscale chirality, ascribed to their pronounced molecular stacking preference on two-dimensional orientations. Significantly, when achiral bipyridine-, melamine-, and imidazole-based molecular binders that could potentially form hydrogen-bonded complexes with these aromatic amino acids were introduced, the induced chiral nanostructures from the resulting coassemblies were observed. Melamine and its derivatives presented an excellent capability to generate ordered supramolecular structures and induce the nanoscale chirality. Assisted by the key duplex hydrogen bonds between the melamine core and serine segments, chiral nanotubes and ribbons were obtained. This study reveals that multiple hydrogen bonds are the prerequisite for inducing the emergence of chiral nanostructures from integrated coassemblies.
开发人工系统以模拟手性的出现对于更好地理解自然界中手性的神秘起源以及指导先进手性材料的设计至关重要。在此，我们提出了一种受 DNA 启发的方法来控制超分子纳米尺度手性在多种氢键自组装中的出现。带有丝氨酸和芳香族结构域的 N 端芳香族氨基酸可以自组装成没有纳米尺度手性的层状微片，这归因于它们在二维方向上强烈的分子堆积偏好。显著的是，当引入非手性的联吡啶、三聚氰胺和咪唑基分子配体，它们可能与这些芳香族氨基酸形成氢键复合物时，从所得共组装体中观察到诱导的手性纳米结构。三聚氰胺及其衍生物具有生成有序超分子结构和诱导纳米尺度手性的优异能力。在三聚氰胺核心和丝氨酸片段之间的关键双螺旋氢键的辅助下，得到了手性纳米管和纳米带。这项研究表明，多个氢键是从集成共组装体中诱导手性纳米结构出现的前提条件。
