Ultra-sensitive vibrational spectroscopy of protein monolayers with plasmonic nanoantenna arrays
Open accessAbstract
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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Plasmonic nanoantennas enhance IR fingerprint absorption by tailored plasmonic resonance.
“artificially structured nanoantenna is demonstrated to enhance the IR fingerprint absorption by tailored plasmonic resonance12,13.”
From Wavelength-multiplexed hook nanoantennas for machine learning enabled mid-infrared spectroscopy (2022) · cites this paper as [13]
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Self-citation
- Authors
- Adato, R., Yanik, A. A., Amsden, J. J., Kaplan, D. L., Omenetto, F. G., Hong, M. K., Erramilli, S., & Altug, H.
- Affiliations
- Boston University (US)
- Departments of aElectrical and Computer Engineering,
- Departments of cBiomedical Engineering and
- Tufts University (US)
- Physics, and
- ORCID
- Venue
- Proceedings of the National Academy of Sciences
- Publisher
- National Academy of Sciences
- Published
- 2009-11-17
- Volume
- 106
- Issue
- 46
- Pages
- 19227-19232
- ISSN
- 0027-8424 (ISSN-L)
- 1091-6490
- PMC
- PMC2770897
- OpenAlex
- W2035669546
- Cited by
- 668
- References
- 31
- Citations by year
- 2026: 19 · 2025: 24 · 2024: 31 · 2023: 29 · 2022: 28 · 2021: 34 · 2020: 39 · 2019: 54 · 2018: 57 · 2017: 69 · 2016: 44 · 2015: 53 · 2014: 48 · 2013: 50 · 2012: 38
- FWCI
- 17.82
- Type
- journal article
- Language
- en
- Open access
- green
- www.ncbi.nlm.nih.gov
- Locations
- Proceedings of the National Academy of Sciences (publishedVersion)
- PubMed Central (publishedVersion)
- PubMed (publishedVersion)
- Infoscience (Ecole Polytechnique Fédérale de Lausanne) (submittedVersion)
- Infoscience (Ecole Polytechnique Fédérale de Lausanne) (submittedVersion, cc-by-nc-nd)
- Topics
- Physical Sciences › Engineering › Biomedical Engineering › Plasmonic and Surface Plasmon Research
- Physical Sciences › Materials Science › Electronic, Optical and Magnetic Materials › Gold and Silver Nanoparticles Synthesis and Applications
- Life Sciences › Biochemistry, Genetics and Molecular Biology › Biophysics › Spectroscopy Techniques in Biomedical and Chemical Research
- Keywords
- plasmonic nanoantenna arrays, protein monolayers, infrared absorption spectroscopy, vibrational spectroscopy, plasmonic enhancement, near-field enhancement, dipolar coupling, zeptomole detection, Fano resonance, non-equilibrium Green's function
- MeSH terms
- Fibroins, Sensitivity and Specificity, Spectrophotometry, Infrared, Spectrum Analysis, Raman, Vibration, Surface Plasmon Resonance, Nanostructures
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