Circular Polarization-Resolved Raman Optical Activity: A Perspective on Chiral Spectroscopies of Vibrational States

Circular Polarization-Resolved Raman Optical Activity: A Perspective on Chiral Spectroscopies of Vibrational States

May 6, 2024 | Engin Er, Tsz Him Chow, Luis M. Liz-Marzán, Nicholas A. Kotov
The article provides a comprehensive overview of circular polarization-resolved Raman optical activity (ROA) and surface-enhanced Raman optical activity (SEROA), highlighting their rapid development and applications in chiral spectroscopies. ROA and SEROA are advanced spectroscopic techniques that enable the direct readout of vibrational energy levels of chiral molecules, crystals, and nanostructured materials, offering high information content and stand-off capabilities. These methods are particularly valuable for studying complex interactions and dynamic interfaces between chiral systems, especially in nano- and biotechnological fields. The article discusses the principles of ROA and SEROA, including their ability to detect differences in the imaginary and real parts of the complex refractive index, leading to circular dichroism (CD) and optical rotatory dispersion (ORD). It also explains how these techniques can be enhanced by plasmonic and semiconductor nanoparticles, which provide strong local electromagnetic fields and amplify weak signals. The authors highlight the importance of chiral phonons, which are long-range coherent vibrations that exhibit strong circular polarization and can be detected using ROA and SEROA. The biological applications of ROA and SEROA are explored, emphasizing their potential for detecting chiral biomolecules in complex biological media. The article discusses the challenges and advancements in achieving reliable and high signal-to-noise ratios in SEROA, as well as the use of chiral nanostructures and plasmonic substrates to enhance sensitivity and specificity. Finally, the article compares ROA, SEROA, and surface-enhanced Raman scattering (SERS), noting their unique advantages and limitations. It concludes with future perspectives, emphasizing the importance of tailoring chiral geometry and improving theoretical models to enhance the performance of SEROA-based platforms. The authors also discuss the potential of 3D chiroptical assemblies and all-dielectric nanomaterials for advancing SEROA in biological applications.The article provides a comprehensive overview of circular polarization-resolved Raman optical activity (ROA) and surface-enhanced Raman optical activity (SEROA), highlighting their rapid development and applications in chiral spectroscopies. ROA and SEROA are advanced spectroscopic techniques that enable the direct readout of vibrational energy levels of chiral molecules, crystals, and nanostructured materials, offering high information content and stand-off capabilities. These methods are particularly valuable for studying complex interactions and dynamic interfaces between chiral systems, especially in nano- and biotechnological fields. The article discusses the principles of ROA and SEROA, including their ability to detect differences in the imaginary and real parts of the complex refractive index, leading to circular dichroism (CD) and optical rotatory dispersion (ORD). It also explains how these techniques can be enhanced by plasmonic and semiconductor nanoparticles, which provide strong local electromagnetic fields and amplify weak signals. The authors highlight the importance of chiral phonons, which are long-range coherent vibrations that exhibit strong circular polarization and can be detected using ROA and SEROA. The biological applications of ROA and SEROA are explored, emphasizing their potential for detecting chiral biomolecules in complex biological media. The article discusses the challenges and advancements in achieving reliable and high signal-to-noise ratios in SEROA, as well as the use of chiral nanostructures and plasmonic substrates to enhance sensitivity and specificity. Finally, the article compares ROA, SEROA, and surface-enhanced Raman scattering (SERS), noting their unique advantages and limitations. It concludes with future perspectives, emphasizing the importance of tailoring chiral geometry and improving theoretical models to enhance the performance of SEROA-based platforms. The authors also discuss the potential of 3D chiroptical assemblies and all-dielectric nanomaterials for advancing SEROA in biological applications.
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