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  • Primer
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Surface-enhanced infrared absorption spectroscopy

Nature Reviews Methods Primers volume 3, Article number: 70 (2023) Cite this article

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Abstract

When molecules are placed at the interface to metals or metal oxides, an increase in their infrared (IR) spectral intensities is observed, a phenomenon termed surface-enhanced infrared absorption (SEIRA). This effect was found initially for polydisperse metal island films with moderate to strong enhancements enabling the detection of IR signals at the monolayer level. Later, the advancement of lithographic techniques gave access to specifically tailored nano-antennas with plasmonic resonances, which provide enhancements by several orders of magnitude, such that a detection in the range of 103 molecules became possible. With the chemical resolution inherent to IR spectroscopy and its non-destructive and label-free nature, the SEIRA effect, therefore, opened the door to a large range of chemical and biophysical applications, which had not been possible earlier without SEIRA’s surface sensitivity and enhancing effect. This Primer describes the mechanisms underlying the SEIRA effect, common methods to fabricate SEIRA-active materials, and the advantages and limitations of this powerful approach. Furthermore, the broad applicability of SEIRA is presented with a particular focus on examples from the fields of analytics, electrochemistry and catalysis as well as biophysical functional investigations, finally concluding on future trends in this vibrant field of research.

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Fig. 1: Mechanism of surface-enhanced infrared absorption (SEIRA).
Fig. 2: Instrumental set-up for FTIR spectroscopy.
Fig. 3: (Electro)Chemical fabrication and functionalization of SEIRA-active materials.
Fig. 4: Data analysis and characteristics of SEIRA.
Fig. 5: Tunable rSEIRA materials for trace analysis and bioanalytic applications.
Fig. 6: Investigating (bio)electrocatalysis using SEIRAS.
Fig. 7: Biofunctional investigations at model membranes using SEIRAS.

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Acknowledgements

The authors thank D. Sinausia and C. Vogt (Technion, Israel) and G. Rose (Johns Hopkins University, USA) for valuable comments. J.K. and J.H. acknowledge the German Research Foundation (DFG) for support via the Sonderforschungsbereich 1078 (SFB 1078) ‘Protonation Dynamics in Protein Function’ (project number 221545957; projects A01, B03, B09). J.K. is further supported by a DFG Individual Research Grant (project number 500707750); J.H. receives additional funding from the SFB 1349 ‘Fluor-Specific Interactions: Fundamentals and Functions’ (project number 387284271 — project C05) and the Cluster of Excellence ‘UniSysCat’ (project number 390540038). K.A. and J.H. further acknowledge funding by DFG HE 206318-1.

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  1. Physics Department, Experimental Molecular Biophysics, Freie Universität Berlin, Berlin, Germany

    Jacek Kozuch, Kenichi Ataka & Joachim Heberle

  2. SupraFAB Research Building, Freie Universität Berlin, Berlin, Germany

    Jacek Kozuch & Joachim Heberle

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Glossary

Affinity tags

Chemical motives or amino acid sequences that have a high affinity for a certain (macro)molecule, such that it binds specifically even in the presence of other molecules.

Changes in dipole moment

The intensity of signals in infrared spectra is dependent on the change in dipole moment during a vibration; on a quantum-mechanical level, this is expressed by the transition dipole moment, a measure for the probability of vibrational excitations.

Lithography

A collection of methods that are used for the fabrication of (nano)scale structures using laser sources (photolithography) or ion/electron beams (scanning lithography) often in combination with stamps or masks.

Localized surface plasmon resonance

(LSPR). A resonance formed by the constructive interference of surface plasmon polaritons that are confined in nano-antennas or between nanoparticles.

Non-resonant SEIRA

(nrSEIRA). Broad spectral infrared surface enhancement obtained via the modulation of the metal’s dielectric function by the vibrations of the adsorbed molecules.

Operando SEIRAS

Operando (or in situ) surface-enhanced infrared absorption spectroscopy (SEIRAS) records spectral changes while a chemical reaction occurs at the metal interface, such that substrates, intermediates and/or products can be detected.

Oscillating dipoles

The charge distribution of molecules can be described by net charge, dipolar charge separation and higher multipoles. During vibrations the net charge remains constant, but the charge separation fluctuates periodically, as in oscillating dipoles.

Resonant SEIRA

(rSEIRA). Narrow spectral infrared surface enhancement via an enhanced near field at the metal surface that is generated through excitation of localized surface plasmon resonances.

SEIRA spectroelectrochemistry

Surface-enhanced infrared absorption (SEIRA) spectra are recorded of processes that are initiated or controlled by the electrochemical potential at a SEIRA-active electrode surface.

Surface-selection rule

Non-resonant surface-enhanced infrared absorption (SEIRA) and resonant SEIRA only enhance the infrared absorption for molecular vibrations with dipole changes along the surface normal, allowing to determine molecular orientations.

Surface plasmon polariton

A quasiparticle describing the coupling of surface plasmons with photons, which propagates along the surface of the material.

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Kozuch, J., Ataka, K. & Heberle, J. Surface-enhanced infrared absorption spectroscopy. Nat Rev Methods Primers 3, 70 (2023). https://doi.org/10.1038/s43586-023-00253-8

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