Measuring optical activity in the far-field from a racemic nanomaterial: Diffraction spectroscopy from plasmonic nanogratings
Royal Society of Chemistry
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Kuppe, C., Zheng, X., Williams, C., Murphy, A., Collins, J., Gordeev, S., Vandenbosch, G., & et al. (2019). Measuring optical activity in the far-field from a racemic nanomaterial: Diffraction spectroscopy from plasmonic nanogratings. Nanoscale Horizons, 4 (5), 1056-1062. https://doi.org/10.1039/c9nh00067d
Recent progress in nanofabrication has redrawn the boundaries of the applicability of chiroptical (chiral optical) effects. Chirality, often expressed as a twist in biomolecules, is crucial for pharmaceuticals, where it can result in extremely different chemical properties. Because chiroptical effects are typically very weak in molecules, plasmonic nanomaterials are often proposed as a promising platform to significantly enhance these effects. Unfortunately, the ideal plasmonic nanomaterial has conflicting requirements: Its chirality should enhance that of the chiral molecules and yet it should have no chiroptical response on its own. Here, we propose a unique reconciliation to satisfy the requirements: A racemic plasmonic nanomaterial, consisting of equal amounts of opposite chiral unit cells. We show how diffraction spectroscopy can be used to unveil the presence of chirality in such racemic nanogratings in the far-field. Our experiments are supported by numerical simulations and yield a circular intensity difference of up to 15%. The physical origin is demonstrated by full wave simulations in combination with a Green's function-group-theory-based analysis. Contributions from Circular Dichroism in the Angular Distribution of Photoelectrons (CDAD) and pseudo/extrinsic chirality are ruled out. Our findings enable the far-field measurement and tuning of racemic nanomaterials, which is crucial for hyper-sensitive chiral molecular characterization.
V. K. V. acknowledges support from the Royal Society through the University Research Fellowships. We acknowledge Royal Society grants CHG\R1\170067, PEF1\170015 and RGF\EA\180228, as well as STFC grant ST/R005842/1 and EPSRC grant EP/L015544/1. C. W. acknowledges financial support from Cancer Research UK (CRUK) Pioneer Award (C55962/A24669) and Wolfson College, Cambridge, UK. C. W. further acknowledges research support from S. Bohndiek, T. Wilkinson and G. Gordon. X. Z. and G. A. E. V. are grateful for the financial support from the FWO (G090017N) and KU Leuven internal research funds (C24/15/015).
UNIVERSITY COLLEGE LONDON (FB EPSRC) (EP/G037256/1)
Cancer Research UK (24669)
External DOI: https://doi.org/10.1039/c9nh00067d
This record's URL: https://www.repository.cam.ac.uk/handle/1810/296441
Attribution 4.0 International
Licence URL: https://creativecommons.org/licenses/by/4.0/