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
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:
- 10500888
- Publisher / Repository:
- Wiley
- 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
-
-
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
-
The accurate detection, classification, and separation of chiral molecules are pivotal for advancing pharmaceutical and biomolecular innovations. Engineered chiral light presents a promising avenue to enhance the interaction between light and matter, offering a noninvasive, high-resolution, and cost-effective method for distinguishing enantiomers. Here, we present a nanostructured platform for surface-enhanced infrared absorption–induced vibrational circular dichroism (VCD) based on an achiral plasmonic system. This platform enables precise measurement, differentiation, and quantification of enantiomeric mixtures, including concentration and enantiomeric excess determination. Our experimental results exhibit a 13 orders of magnitude higher detection sensitivity for chiral enantiomers compared to conventional VCD spectroscopic techniques, accounting for respective path lengths and concentrations. The tunable spectral characteristics of this achiral plasmonic system facilitate the detection of a diverse range of chiral compounds. The platform’s simplicity, tunability, and exceptional sensitivity holds remarkable potential for enantiomer classification in drug design, pharmaceuticals, and biological applications.more » « less
-
Abstract The identification of Chiral molecules is essential in pharmaceutical and food science. However, conventional methods are complex and cost‐prohibitive. This study introduces a sustainable method using hydroxypropyl cellulose (HPC) gel to identify amino acids enantiomers, such as phenylalanine and alanine, through visible light. By integrating the structural color properties of HPC, this research demonstrates the HPC gel's capability to distinguish L (Levo)‐phenylalanine (L‐Phe), D (Dextro)‐phenylalanine (D‐Phe), and DL (racemic mixture)‐phenylalanine (DL‐Phe) supplemented with visible circular dichroism (CD) spectra or hydrochloric acid (HCl) as visual indicators. Similar chiral sensing results are observed with D‐alanine, L‐alanine, and DL‐alanine. Unlike traditional UV‐based detection requiring expensive equipment, this approach simplifies the process while maintaining sensitivity. Varying phenylalanine concentrations altered the CD response without disrupting the gel's helical structure, and color changes in response to HCl addition facilitated visual identification of enantiomers. Furthermore, adding various salts generates colorful HPC/Phe gels, demonstrating their suitability for 3D printing. Meanwhile, the HPC gels remained functional for three months, indicating long‐term stability. These advancements are significant for pharmaceutical and biotechnological industries, facilitating efficient low‐concentration chirality detection (0.2 wt.%). Continued development and refinement of this technology are expected to expand its applications and improve analytical capabilities for future chirality‐related studies and photonic gel 3D printing.more » « less
-
Ligand‐assisted perovskite nanoclusters (PNCs) have been synthesized using oleylamine and L‐ or D‐cysteine as confirmed based on their characteristic electronic absorption bands around 430 nm based on ultraviolet‐visible spectra. Circular dichroism (CD) spectra show distinct chiroptical bands in the 430–440 nm region, revealing the chirality of the PNCs. Interestingly, the sign of the CD signal is always negative, independent of the chirality for L‐ or D‐cystine. This 430–440 nm CD band is tentatively attributed to the formation of new chiral stereocenters within the PNCs with an uneven ratio of two enantiomers induced by the asymmetric liquid–liquid interface from the solvent and antisolvent used during synthesis.more » « less
An official website of the United States government

