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具有手性连续体的光活性领结型纳米组件。

Photonically active bowtie nanoassemblies with chirality continuum.

作者信息

Kumar Prashant, Vo Thi, Cha Minjeong, Visheratina Anastasia, Kim Ji-Young, Xu Wenqian, Schwartz Jonathan, Simon Alexander, Katz Daniel, Nicu Valentin Paul, Marino Emanuele, Choi Won Jin, Veksler Michael, Chen Si, Murray Christopher, Hovden Robert, Glotzer Sharon, Kotov Nicholas A

机构信息

Department of Chemical Engineering, University of Michigan, Ann Arbor, MI, USA.

Biointerfaces Institute, University of Michigan, Ann Arbor, MI, USA.

出版信息

Nature. 2023 Mar;615(7952):418-424. doi: 10.1038/s41586-023-05733-1. Epub 2023 Mar 15.

Abstract

Chirality is a geometrical property described by continuous mathematical functions. However, in chemical disciplines, chirality is often treated as a binary left or right characteristic of molecules rather than a continuity of chiral shapes. Although they are theoretically possible, a family of stable chemical structures with similar shapes and progressively tuneable chirality is yet unknown. Here we show that nanostructured microparticles with an anisotropic bowtie shape display chirality continuum and can be made with widely tuneable twist angle, pitch, width, thickness and length. The self-limited assembly of the bowties enables high synthetic reproducibility, size monodispersity and computational predictability of their geometries for different assembly conditions. The bowtie nanoassemblies show several strong circular dichroism peaks originating from absorptive and scattering phenomena. Unlike classical chiral molecules, these particles show a continuum of chirality measures that correlate exponentially with the spectral positions of the circular dichroism peaks. Bowtie particles with variable polarization rotation were used to print photonically active metasurfaces with spectrally tuneable positive or negative polarization signatures for light detection and ranging (LIDAR) devices.

摘要

手性是一种由连续数学函数描述的几何性质。然而,在化学学科中,手性通常被视为分子的二元左或右特征,而不是手性形状的连续性。尽管从理论上来说是可能的,但一类具有相似形状和可逐步调节手性的稳定化学结构仍然未知。在此,我们展示了具有各向异性领结形状的纳米结构微粒表现出手性连续体,并且可以制成具有广泛可调的扭转角、螺距、宽度、厚度和长度。领结的自限性组装实现了高合成再现性、尺寸单分散性以及针对不同组装条件下其几何形状的计算可预测性。领结纳米组装体显示出几个源自吸收和散射现象的强圆二色性峰。与经典手性分子不同,这些粒子表现出手性度量的连续体,其与圆二色性峰的光谱位置呈指数相关。具有可变偏振旋转的领结粒子被用于打印具有光谱可调正或负偏振特征的光活性超表面,用于光探测和测距(激光雷达)设备。

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