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      Chirality detection of enantiomers using twisted optical metamaterials

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          Abstract

          Many naturally occurring biomolecules, such as amino acids, sugars and nucleotides, are inherently chiral. Enantiomers, a pair of chiral isomers with opposite handedness, often exhibit similar physical and chemical properties due to their identical functional groups and composition, yet show different toxicity to cells. Detecting enantiomers in small quantities has an essential role in drug development to eliminate their unwanted side effects. Here we exploit strong chiral interactions with plasmonic metamaterials with specifically designed optical response to sense chiral molecules down to zeptomole levels, several orders of magnitude smaller than what is typically detectable with conventional circular dichroism spectroscopy. In particular, the measured spectra reveal opposite signs in the spectral regime directly associated with different chiral responses, providing a way to univocally assess molecular chirality. Our work introduces an ultrathin, planarized nanophotonic interface to sense chiral molecules with inherently weak circular dichroism at visible and near-infrared frequencies.

          Abstract

          Here Zhao et al. use twisted metamaterials to drastically enhance chiral responses through strong near-field interactions, and sense the chirality down to zeptomoles of molecules, orders of magnitude smaller than what is detectable with conventional circular dichroism spectroscopy.

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          Most cited references21

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          Gold helix photonic metamaterial as broadband circular polarizer.

          We investigated propagation of light through a uniaxial photonic metamaterial composed of three-dimensional gold helices arranged on a two-dimensional square lattice. These nanostructures are fabricated via an approach based on direct laser writing into a positive-tone photoresist followed by electrochemical deposition of gold. For propagation of light along the helix axis, the structure blocks the circular polarization with the same handedness as the helices, whereas it transmits the other, for a frequency range exceeding one octave. The structure is scalable to other frequency ranges and can be used as a compact broadband circular polarizer.
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            Twisted optical metamaterials for planarized ultrathin broadband circular polarizers.

            Optical metamaterials are usually based on planarized, complex-shaped, resonant nano-inclusions. Three-dimensional geometries may provide a wider set of functionalities, including broadband chirality to manipulate circular polarization at the nanoscale, but their fabrication becomes challenging as their dimensions get smaller. Here we introduce a new paradigm for the realization of optical metamaterials, showing that three-dimensional effects may be obtained without complicated inclusions, but instead by tailoring the relative orientation within the lattice. We apply this concept to realize planarized, broadband bianisotropic metamaterials as stacked nanorod arrays with a tailored rotational twist. Because of the coupling among closely spaced twisted plasmonic metasurfaces, metamaterials realized with conventional lithography may effectively operate as three-dimensional helical structures with broadband bianisotropic optical response. The proposed concept is also shown to relax alignment requirements common in three-dimensional metamaterial designs. The realized sample constitutes an ultrathin, broadband circular polarizer that may be directly integrated within nanophotonic systems.
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              DNA-based Self-Assembly of Chiral Plasmonic Nanostructures with Tailored Optical Response

              Surface plasmon resonances generated in metallic nanostructures can be utilized to tailor electromagnetic fields. The precise spatial arrangement of such structures can result in surprising optical properties that are not found in any naturally occurring material. Here, the designed activity emerges from collective effects of singular components equipped with limited individual functionality. Top-down fabrication of plasmonic materials with a predesigned optical response in the visible range by conventional lithographic methods has remained challenging due to their limited resolution, the complexity of scaling, and the difficulty to extend these techniques to three-dimensional architectures. Molecular self-assembly provides an alternative route to create such materials which is not bound by the above limitations. We demonstrate how the DNA origami method can be used to produce plasmonic materials with a tailored optical response at visible wavelengths. Harnessing the assembly power of 3D DNA origami, we arranged metal nanoparticles with a spatial accuracy of 2 nm into nanoscale helices. The helical structures assemble in solution in a massively parallel fashion and with near quantitative yields. As a designed optical response, we generated giant circular dichroism and optical rotary dispersion in the visible range that originates from the collective plasmon-plasmon interactions within the nanohelices. We also show that the optical response can be tuned through the visible spectrum by changing the composition of the metal nanoparticles. The observed effects are independent of the direction of the incident light and can be switched by design between left- and right-handed orientation. Our work demonstrates the production of complex bulk materials from precisely designed nanoscopic assemblies and highlights the potential of DNA self-assembly for the fabrication of plasmonic nanostructures.
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                Author and article information

                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group
                2041-1723
                25 January 2017
                2017
                : 8
                : 14180
                Affiliations
                [1 ]Department of Electrical and Computer Engineering, The University of Texas at Austin, 1 University Station , Austin, Texas 78712, USA
                [2 ]Department of Electrical Engineering, Amirkabir University of Technology , 424 Hafez Avenue, Tehran 15875-4413, Iran
                [3 ]Department of Physics, The University of Texas at Austin, 1 University Station , Austin, Texas 78712, USA
                [4 ]Department of Physics, Beijing Normal University , 19 Xinjiekou Outer Street, Beijing 100875, China
                Author notes
                Article
                ncomms14180
                10.1038/ncomms14180
                5288493
                28120825
                031e58cf-8009-46f8-aa13-fd180643978a
                Copyright © 2017, The Author(s)

                This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article's Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/

                History
                : 15 January 2016
                : 06 December 2016
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