Ultrasensitive Raman Detection of Biomolecular Conformation at the Attomole Scale using Chiral Nanophotonics
Language English Country Germany Media print-electronic
Document type Journal Article, Research Support, Non-U.S. Gov't
Grant support
James Watt Nanofabrication Centre
RF-2019-023
Leverhulme Trust
23-08509S
Grantová Agentura České Republiky
EP/S029168/1
Engineering and Physical Sciences Research Council
EP/S012745/1
Engineering and Physical Sciences Research Council
EP/S001514/1
EPSRC Centre for Doctoral Training in Medical Imaging
- Keywords
- Plasmonics, SERS, chirality, enantiomer, super chirality optical chirality,
- MeSH
- Metal Nanoparticles chemistry MeSH
- Molecular Conformation MeSH
- Nanotechnology methods MeSH
- Peptides chemistry MeSH
- Spectrum Analysis, Raman * methods MeSH
- Gold chemistry MeSH
- Publication type
- Journal Article MeSH
- Research Support, Non-U.S. Gov't MeSH
- Names of Substances
- Peptides MeSH
- Gold MeSH
Understanding the function of a biomolecule hinges on its 3D conformation or secondary structure. Chirally sensitive, optically active techniques based on the differential absorption of UV-vis circularly polarized light excel at rapid characterisation of secondary structures. However, Raman spectroscopy, a powerful method for determining the structure of simple molecules, has limited capacity for structural analysis of biomolecules because of intrinsically weak optical activity, necessitating millimolar (mM) sample quantities. A breakthrough is presented for utilising Raman spectroscopy in ultrasensitive biomolecular conformation detection, surpassing conventional Raman optical activity by 15 orders of magnitude. This strategy combines chiral plasmonic metasurfaces with achiral molecular Raman reporters and enables the detection of different conformations (α-helix and random coil) of a model peptide (poly-L/D-lysine) at the ≤attomole level (monolayer). This exceptional sensitivity stems from the ability to detect local, molecular-scale changes in the electromagnetic (EM) environment of a chiral nanocavity induced by the presence of biomolecules using molecular Raman reporters. Further signal enhancement is achieved by incorporating achiral Au nanoparticles. The introduction of the nanoparticles creates highly localized regions of extreme optical chirality. This approach, which exploits Raman, a generic phenomenon, paves the way for next-generation technologies for the ultrasensitive detection of diverse biomolecular structures.
James Watt School of Engineering Rankine Building University of Glasgow Glasgow G12 8QQ UK
School of Chemistry Joseph Black Building University of Glasgow Glasgow G12 8QQ UK
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