Biomacromolecular stereostructure mediates mode hybridization in chiral plasmonic nanostructures

Calum Jack, Affar S. Karimullah, Ross Leyman, Ryan Tullius, Vincent M. Rotello, Graeme Cooke, Nikolaj Gadegaard , Laurence D. Barron, Malcolm Kadodwala

Research output: Contribution to journalArticle

20 Citations (Scopus)

Abstract

The refractive index sensitivity of plasmonic fields has been exploited for over 20 years in analytical technologies. While this sensitivity can be used to achieve attomole detection levels, they are in essence binary measurements that sense the presence/absence of a predetermined analyte. Using plasmonic fields, not to sense effective refractive indices but to provide more "granular" information about the structural characteristics of a medium, provides a more information rich output, which affords opportunities to create new powerful and flexible sensing technologies not limited by the need to synthesize chemical recognition elements. Here we report a new plasmonic phenomenon that is sensitive to the biomacromolecular structure without relying on measuring effective refractive indices. Chiral biomaterials mediate the hybridization of electric and magnetic modes of a chiral solid-inverse plasmonic structure, resulting in a measurable change in both reflectivity and chiroptical properties. The phenomenon originates from the electric-dipole–magnetic-dipole response of the biomaterial and is hence sensitive to biomacromolecular secondary structure providing unique fingerprints of α-helical, β-sheet, and disordered motifs. The phenomenon can be observed for subchiral plasmonic fields (i.e., fields with a lower chiral asymmetry than circularly polarized light) hence lifting constraints to engineer structures that produce fields with enhanced chirality, thus providing greater flexibility in nanostructure design. To demonstrate the efficacy of the phenomenon, we have detected and characterized picogram quantities of simple model helical biopolymers and more complex real proteins.
LanguageEnglish
Pages5806–5814
Number of pages9
JournalNano Letters
Volume16
Issue number9
DOIs
Publication statusPublished - 22 Aug 2016

Fingerprint

Nanostructures
Refractive index
Biocompatible Materials
refractivity
Biomaterials
Biopolymers
Chirality
biopolymers
sensitivity
Light polarization
magnetic dipoles
chirality
polarized light
electric dipoles
engineers
flexibility
asymmetry
proteins
Proteins
reflectance

Keywords

  • chiral plasmonics
  • plasmonic hybridization
  • biosensing
  • optically active second harmonic generation

Cite this

Jack, C., Karimullah, A. S., Leyman, R., Tullius, R., Rotello, V. M., Cooke, G., ... Kadodwala, M. (2016). Biomacromolecular stereostructure mediates mode hybridization in chiral plasmonic nanostructures. Nano Letters, 16(9), 5806–5814. https://doi.org/10.1021/acs.nanolett.6b02549
Jack, Calum ; Karimullah, Affar S. ; Leyman, Ross ; Tullius, Ryan ; Rotello, Vincent M. ; Cooke, Graeme ; Gadegaard , Nikolaj ; Barron, Laurence D. ; Kadodwala, Malcolm . / Biomacromolecular stereostructure mediates mode hybridization in chiral plasmonic nanostructures. In: Nano Letters. 2016 ; Vol. 16, No. 9. pp. 5806–5814.
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Jack, C, Karimullah, AS, Leyman, R, Tullius, R, Rotello, VM, Cooke, G, Gadegaard , N, Barron, LD & Kadodwala, M 2016, 'Biomacromolecular stereostructure mediates mode hybridization in chiral plasmonic nanostructures' Nano Letters, vol. 16, no. 9, pp. 5806–5814. https://doi.org/10.1021/acs.nanolett.6b02549

Biomacromolecular stereostructure mediates mode hybridization in chiral plasmonic nanostructures. / Jack, Calum; Karimullah, Affar S.; Leyman, Ross; Tullius, Ryan; Rotello, Vincent M.; Cooke, Graeme; Gadegaard , Nikolaj ; Barron, Laurence D.; Kadodwala, Malcolm .

In: Nano Letters, Vol. 16, No. 9, 22.08.2016, p. 5806–5814.

Research output: Contribution to journalArticle

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AU - Jack, Calum

AU - Karimullah, Affar S.

AU - Leyman, Ross

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AU - Rotello, Vincent M.

AU - Cooke, Graeme

AU - Gadegaard , Nikolaj

AU - Barron, Laurence D.

AU - Kadodwala, Malcolm

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AB - The refractive index sensitivity of plasmonic fields has been exploited for over 20 years in analytical technologies. While this sensitivity can be used to achieve attomole detection levels, they are in essence binary measurements that sense the presence/absence of a predetermined analyte. Using plasmonic fields, not to sense effective refractive indices but to provide more "granular" information about the structural characteristics of a medium, provides a more information rich output, which affords opportunities to create new powerful and flexible sensing technologies not limited by the need to synthesize chemical recognition elements. Here we report a new plasmonic phenomenon that is sensitive to the biomacromolecular structure without relying on measuring effective refractive indices. Chiral biomaterials mediate the hybridization of electric and magnetic modes of a chiral solid-inverse plasmonic structure, resulting in a measurable change in both reflectivity and chiroptical properties. The phenomenon originates from the electric-dipole–magnetic-dipole response of the biomaterial and is hence sensitive to biomacromolecular secondary structure providing unique fingerprints of α-helical, β-sheet, and disordered motifs. The phenomenon can be observed for subchiral plasmonic fields (i.e., fields with a lower chiral asymmetry than circularly polarized light) hence lifting constraints to engineer structures that produce fields with enhanced chirality, thus providing greater flexibility in nanostructure design. To demonstrate the efficacy of the phenomenon, we have detected and characterized picogram quantities of simple model helical biopolymers and more complex real proteins.

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Jack C, Karimullah AS, Leyman R, Tullius R, Rotello VM, Cooke G et al. Biomacromolecular stereostructure mediates mode hybridization in chiral plasmonic nanostructures. Nano Letters. 2016 Aug 22;16(9):5806–5814. https://doi.org/10.1021/acs.nanolett.6b02549