Enhancing Volumetric Optical Chirality through 2D-3D Structural Design Evolution

TL;DR

This paper introduces a new figure of merit for designing 3D chiral nanostructures that enhances optical chirality and sensing volume, significantly improving circular dichroism detection capabilities.

Contribution

It presents a systematic design framework and a novel FOM to optimize 3D chiral structures for improved chiroptical sensing performance.

Findings

Optimized triple-strand helix achieved a FOM of 2.43×10^10 nm^3.

FOM correlates strongly (R^2=0.9256) with analyte CD signal.

Structural evolution enhances sensing volume without compromising field enhancement.

Abstract

Circular dichroism (CD) sensing plays a pivotal role in probing molecular chirality in biomedical sciences. However, engineering superchiral electromagnetic fields that can reliably amplify the faint signatures of chiral analytes remains profoundly challenging. Central to this difficulty is the need to balance two competing demands: maximizing the enhancement of chiral fields while maintaining a sufficiently large interaction volume for effective molecular interrogation. Here, we introduce a figure of merit (FOM) that captures the enhancement and spatial coverage of superchiral fields to benchmark different chiral-field configurations. We examine the effects of helix-geometry evolution on the FOM, including 2D to 3D chirality induction, winding-number escalation, helical-order enhancement, and transverse dilation. By tuning these structural degrees of freedom, the sensing volume can be enlarged without compromising the distribution and enhancement strength of fields. The optimized triple-strand helix markedly enhanced the analyte CD signal, yielding a FOM of 2.43*10^10 nm3, which surpassed prior 2D and 3D configurations by over an order of magnitude. The proposed FOM exhibits a strong linear correlation (R^2 = 0.9256) with the analyte CD signal. Our findings provide a systematic design framework for 3D chiral structures and a robust metric for assessing their chiroptical sensing performance, particularly in scenarios involving clusters of randomly oriented small molecules or a large chiral molecule.