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Ultra-sensitive vibrational spectroscopy of protein monolayers with plasmonic nanoantenna arrays.

Publication ,  Journal Article
Adato, R; Yanik, AA; Amsden, JJ; Kaplan, DL; Omenetto, FG; Hong, MK; Erramilli, S; Altug, H
Published in: Proceedings of the National Academy of Sciences of the United States of America
November 2009

Infrared absorption spectroscopy enabling direct access to vibrational fingerprints of the molecular structure is a powerful method for functional studies of bio-molecules. Although the intrinsic absorption cross-sections of IR active modes of proteins are nearly 10 orders of magnitude larger than the corresponding Raman cross-sections, they are still small compared to that of fluorescence-label based methods. Here, we developed a new tool based on collective excitation of plasmonic nanoantenna arrays and demonstrated direct detection of vibrational signatures of single protein monolayers. We first tailored the geometry of individual nanoantennas to form resonant structures that match the molecular vibrational modes. The tailored nanoantennas are then arranged in such a way that their in-phase dipolar coupling leads to a collective excitation of the ensemble with strongly enhanced near fields. The combined collective and individual plasmonic responses of the antenna array play a critical role in attaining signal enhancement factors of 10(4)-10(5). We achieved measurement of the vibrational spectra of proteins at zeptomole levels for the entire array, corresponding to only 145 molecules per antenna. The near-field nature of the plasmonic enhancement of the absorption signals is demonstrated with progressive loading of the nanoantennas with varying protein film thicknesses. Finally, an advanced model based on nonequilibrium Green's function formalism is introduced, which explains the observed Fano-type absorption line-shapes and tuning of the absorption strengths with the antenna resonance.

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Published In

Proceedings of the National Academy of Sciences of the United States of America

DOI

EISSN

1091-6490

ISSN

0027-8424

Publication Date

November 2009

Volume

106

Issue

46

Start / End Page

19227 / 19232

Related Subject Headings

  • Vibration
  • Surface Plasmon Resonance
  • Spectrum Analysis, Raman
  • Spectrophotometry, Infrared
  • Sensitivity and Specificity
  • Nanostructures
  • Fibroins
 

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Adato, R., Yanik, A. A., Amsden, J. J., Kaplan, D. L., Omenetto, F. G., Hong, M. K., … Altug, H. (2009). Ultra-sensitive vibrational spectroscopy of protein monolayers with plasmonic nanoantenna arrays. Proceedings of the National Academy of Sciences of the United States of America, 106(46), 19227–19232. https://doi.org/10.1073/pnas.0907459106
Adato, Ronen, Ahmet A. Yanik, Jason J. Amsden, David L. Kaplan, Fiorenzo G. Omenetto, Mi K. Hong, Shyamsunder Erramilli, and Hatice Altug. “Ultra-sensitive vibrational spectroscopy of protein monolayers with plasmonic nanoantenna arrays.Proceedings of the National Academy of Sciences of the United States of America 106, no. 46 (November 2009): 19227–32. https://doi.org/10.1073/pnas.0907459106.
Adato R, Yanik AA, Amsden JJ, Kaplan DL, Omenetto FG, Hong MK, et al. Ultra-sensitive vibrational spectroscopy of protein monolayers with plasmonic nanoantenna arrays. Proceedings of the National Academy of Sciences of the United States of America. 2009 Nov;106(46):19227–32.
Adato, Ronen, et al. “Ultra-sensitive vibrational spectroscopy of protein monolayers with plasmonic nanoantenna arrays.Proceedings of the National Academy of Sciences of the United States of America, vol. 106, no. 46, Nov. 2009, pp. 19227–32. Epmc, doi:10.1073/pnas.0907459106.
Adato R, Yanik AA, Amsden JJ, Kaplan DL, Omenetto FG, Hong MK, Erramilli S, Altug H. Ultra-sensitive vibrational spectroscopy of protein monolayers with plasmonic nanoantenna arrays. Proceedings of the National Academy of Sciences of the United States of America. 2009 Nov;106(46):19227–19232.
Journal cover image

Published In

Proceedings of the National Academy of Sciences of the United States of America

DOI

EISSN

1091-6490

ISSN

0027-8424

Publication Date

November 2009

Volume

106

Issue

46

Start / End Page

19227 / 19232

Related Subject Headings

  • Vibration
  • Surface Plasmon Resonance
  • Spectrum Analysis, Raman
  • Spectrophotometry, Infrared
  • Sensitivity and Specificity
  • Nanostructures
  • Fibroins