Li Xuecong, Pujari Sidharam P, van der Gucht Jasper, Zuilhof Han, Ruggeri Francesco Simone
Laboratory of Organic Chemistry, Wageningen University, Wageningen, the Netherlands.
Physical Chemistry and Soft Matter, Wageningen University, Wageningen, the Netherlands.
Nat Commun. 2025 Jul 22;16(1):6761. doi: 10.1038/s41467-025-62041-0.
Chirality plays a critical role in the structure and function of natural and synthetic polymers, impacting their mechanical, optical, and electronic properties. However, a comprehensive understanding of the hierarchical emergence of chirality from monomers to macromolecular assemblies remains elusive, largely because of current limitations in studying their chemical-structural properties at the nanoscale. Here, we unravel the emergence of different forms of chirality from small molecules to their resulting polymers and supramolecular assemblies. We leverage bulk spectroscopic methods combined with the development of acoustical-mechanical suppressed infrared nanospectroscopy, to empower chemical-structural analysis of single-polymer chains. This ultra-high sensitivity allows identifying key functional groups as a signature for different forms of chirality: CH groups for central chirality in small molecules; C=O groups for backbone and supramolecular chirality in heterogeneous polymers. This work opens a new single-molecule chemical angle of observation into chirality and (bio)-polymers for the rational design in material science, biotechnology, and medicine.
手性在天然和合成聚合物的结构与功能中起着关键作用，影响着它们的力学、光学和电子性质。然而，对于从单体到大分子聚集体手性的分级出现的全面理解仍然难以捉摸，这主要是由于目前在纳米尺度研究其化学结构性质方面存在局限性。在这里，我们揭示了从小分子到其生成的聚合物和超分子聚集体中不同形式手性的出现。我们利用体相光谱方法并结合声学机械抑制红外纳米光谱的发展，来加强对单聚合物链的化学结构分析。这种超高灵敏度使得能够识别关键官能团作为不同形式手性的特征：小分子中中心手性的CH基团；异质聚合物中主链和超分子手性的C=O基团。这项工作为材料科学、生物技术和医学中的合理设计开辟了一个关于手性和（生物）聚合物全新的单分子化学观察视角。
