skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Enantiomer‐Selective Molecular Sensing in the Nonlinear Optical Regime via Upconverting Chiral Metamaterials
Abstract Enantiomers are chiral isomers in which the isomer's structure itself and its mirror image cannot be superimposed on each other. Enantiomer selective sensing is critical as enantiomers exhibit distinct functionalities to their mirror image. Discriminating between enantiomers by optical methods has been widely used as these techniques provide nondestructive characterization, however, they are constrained by the intrinsically small chirality of the molecules. Here, a method to effectively discriminate chiral analytes in the nonlinear regime is demonstrated, which is facilitated by an upconverting chiral plasmonic metamaterial. The different handedness of the chiral molecules interacts with the chiral metamaterial platform, which leads to a change in the circular dichroism of the chiral metamaterial in the near‐infrared region. The contrast of the circular dichroism is identified by the upconverted signal in the visible region.  more » « less
Award ID(s):
2004749
PAR ID:
10369382
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Advanced Functional Materials
Volume:
32
Issue:
43
ISSN:
1616-301X
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract More than half of pharmaceutical drugs in use are chiral, necessitating accurate techniques for their characterization. Enantiomers, molecules with mirrored symmetry, often exhibit similar physical traits but possess distinct chemical and biological implications. This study harnesses the strong light‐matter interaction induced by “superchiral” light to perform Surface‐Enhanced Infrared Absorption (SEIRA) induced vibrational circular dichroism measurements in the mid‐infrared spectral region. Utilizing a nanopatterned pixelated array of achiral plasmonic nanostructures, the system allows unique identification of enantiomers and biomolecules. Tunability of plasmon resonance facilitates spectral variation of the optical chirality over a wide infrared range, enabling development of a unique chiral “barcoding” scheme to distinguish chiral molecules based on their infrared fingerprint. This simple, yet robust sensor presents a low‐cost solution for chiral mapping of drugs and biomolecules. 
    more » « less
  2. Abstract Over the past two decades, metamaterials have led to an increasing number of biosensing and nanophotonic applications due to the possibility of a careful control of light propagating through subwavelength features. Chiral nanostructures (characterized by the absence of any mirror symmetry), in particular, give rise to unique chiro‐optical properties such as circular dichroism and optical activity. Here, a gyroid optical metamaterial with a periodicity of 65 nm exhibiting a strong circular dichroism at visible wavelengths is presented. This bottom‐up approach, based on metallic replication of the gyroid morphology in triblock terpolymer films, generates a large area of periodic optical metamaterials. A strong circular dichroism in gold and silver gyroid metamaterials at visible wavelengths is observed. It is shown that the circular dichroism is inherently linked to the handedness of the gyroid nanostructure and its tuneability is demonstrated. The optical effects are discussed and compared to other existing systems, showing the potential of bottom‐up approaches for large‐scale circular filters and chiral sensing. 
    more » « less
  3. Abstract Optical chiral imaging, as an important tool in chemical and biological analysis, has recently undergone a revolution with the development of chiral metamaterials and metasurfaces. However, the existing chiral imaging approaches based on metamaterials or metasurfaces can only display binary images with 1 bit pixel depth having either black or white pixels. Here, the unique chiral grayscale imaging based on plasmonic metasurfaces of stepped V‐shaped nanoapertures is reported with both high circular dichroism and large polarization linearity in transmission. By interlacing two subarrays of chiral nanoaperture enantiomers into one metasurface, two specific linear polarization profiles are independently generated in transmission under different incident handedness, which can then be converted into two distinct intensity profiles for demonstrating spin‐controlled grayscale images with 8 bit pixel depth. The proposed chiral grayscale imaging approach with subwavelength spatial resolution and high data density provides a versatile platform for many future applications in image encryption and decryption, dynamic display, advanced chiroptical sensing, and optical information processing. 
    more » « less
  4. Abstract Detection and identification of chiral molecules are important for pharmaceutical industry, clinical analysis, and food analysis. Here, chiral molecular sensing based on spatially selective coupling between achiral metasurface and chiral molecules is demonstrated. The designed achiral metasurface exhibits strong optical chirality and electric field with dissymmetric distribution, and chiral molecules are selectively placed over the area with large optical chirality to form the coupled metasurface-molecule system with circular dichroism (CD) response for chiral molecular sensing. The CD spectra of the metasurface coupled with pure D-alanine enantiomer, L-alanine enantiomer and their mixtures are examined. The linear relationship between the peak CD value and the enantiomeric excess is demonstrated for the detection and identification of pure enantiomers and their mixtures. Furthermore, the CD response of the coupled system shows potential for the sensing of molar concentration of chiral molecules. Moreover, the effect of spatial location of molecules on the CD response is analyzed to show potential for position sensing of chiral molecules. These results of chiral molecular sensing with achiral metasurface offer new opportunities for advancing biomolecular sensing applications. 
    more » « less
  5. Abstract Synthetic chiral platforms can be a powerful platform for enantioselective interactions, especially when coupled with redox‐mediated electrochemical processes. While metallopolymers are versatile platforms for molecularly selective binding, their application for chiral applications is limited. In particular, the recognition and separation of biologically relevant chiral molecules can be key for biomanufacturing and diagnostics. Here, the design of chiral redox‐polymers enables electrochemically‐controlled enantioselective interactions, and supramolecular chirality is leveraged for enhancing recognition towards target enantiomers. Chiral redox‐metallopolymers are synthesized based on Ugi's amine‐inspired chiral monomers, and their enantioselective recognition toward ionic enantiomers such as tryptophan and naproxen is demonstrated, with higher enanhcement provided by the chiral redox‐polymer over the single‐site, chiral building bloack itelf. 2D nuclear magnetic resonance spectroscopy and solid‐state circular dichroism support the emergence of supramolecular chirality resulting from the intramolecular interaction between the ferrocene and the alkyl group in the backbone. The half potential shift of the redox‐polymers behaves linearly from 0% to 100%eel‐tryptophan to enable enantiomer quantification. Investigation on solvent polarity and pH effect reveal that the enantioselective mechanism is attributed to the subtle balance between hydrogen bonding and π–π interaction. This study highlights the potential of chiral redox‐metallopolymers as platforms for electrochemically‐modulated enantioselective interactions towards a range of amino acids and pharmaceutical carboxylates. 
    more » « less