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Combining surface-accessible Ag and Au colloidal nanomaterials with SERS for in situ analysis of molecule–metal interactions in complex solution environments

Nature Protocols volume 18, pages 2717–2744 (2023)Cite this article

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Abstract

The interactions between molecules and noble metal nanosurfaces play a central role in many areas of nanotechnology. The surface chemistry of noble metal surfaces under ideal, clean conditions has been extensively studied; however, clean conditions are seldom met in real-world applications. We developed a sensitive and robust characterization technique for probing the surface chemistry of nanomaterials in the complex environments that are directly relevant to their applications. Surface-enhanced Raman spectroscopy (SERS) can be used to probe the interaction of plasmonic nanoparticles with light to enhance the Raman signals of molecules near the surface of nanoparticles. Here, we explain how to couple SERS with surface-accessible plasmonic-enhancing substrates, which are capped with weakly adsorbing capping ligands such as citrate and chloride ions, to allow molecule–metal interactions to be probed in situ and in real time, thus providing information on the surface orientation and the formation and breaking of chemical bonds. The procedure covers the synthesis and characterization of surface-accessible colloids, the preliminary SERS screening with agglomerated colloids, the synthesis and characterization of interfacial nanoparticle assemblies, termed metal liquid-like films, and the in situ biphasic SERS analysis with metal liquid-like films. The applications of the approach are illustrated using two examples: the probing of π–metal interactions and that of target/ligand–particle interactions on hollow bimetallic nanostars. This protocol, from the initial synthesis of the surface-accessible plasmonic nanoparticles to the final in situ biphasic SERS analysis, requires ~14 h and is ideally suited to users with basic knowledge in performing Raman spectroscopy and wet synthesis of metal nanoparticles.

Key points

  • This protocol covers the synthesis of three types of modifier-free and surface-accessible nanoparticle colloids and of interfacial nanoparticle assemblies (termed metal liquid-like films) as well as their characterization using surface-enhanced Raman spectroscopy.

  • The plasmonic nanomaterials enable the characterization of molecule–metal interactions in complex environments, avoiding the typical passivation of nanomaterials when using surface-adsorbed molecular modifiers.

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Fig. 1: Comparison of SERS with other techniques for surface chemistry analysis.
Fig. 2: Overview of the technique for applying SERS in surface chemistry analysis.
Fig. 3: Representative characterization results of CRSC, CRGC and BRSC.
Fig. 4: Photographs of MeLLFs shaken to different extents.
Fig. 5: A representative sample of a nanoparticle–polymer film formed from a CRGC MeLLF.
Fig. 6: SERS setup for analyzing MeLLFs.
Fig. 7: The effect of container hydrophobicity on the appearance of MeLLFs.
Fig. 8: SERS studies of π–metal interactions between naphthalene and Ag, Au MeLLFs.
Fig. 9: SERS analysis of Ag–Au hollow bimetallic nanostars.

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Data availability

The main data discussed in this protocol are available in the supporting primary research papers17,20,22. The raw datasets are too large to be publicly shared but are available for research purposes from the corresponding authors upon reasonable request.

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Acknowledgements

C.L., Z.Y. and Y.X. acknowledge the University Special Research Scholarship (Queen’s University Belfast) for support. S.E.J.B. acknowledges the Engineering and Physical Sciences Research Council (EPSRC) (grant EP/P034063/1) for support. Y.X. acknowledges The Leverhulme Trust Early Career Fellowship (grant ECF2020703) and RSC Researcher Mobility Grant (grant no. RM1602-4142) for support. Y.Z. acknowledges the Chinese Scholarship Council (202008370188) for support.

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Author notes

  1. Chunchun Li

    Present address: Institute of Photochemistry and Photofunctional Materials, University of Shanghai for Science and Technology, Shanghai, China

  2. Yikai Xu

    Present address: Key Laboratory for Advanced Materials and Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Chemistry and Molecular Engineering, East China University of Science & Technology, Shanghai, China

Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, Queen’s University Belfast, Belfast, UK

    Chunchun Li, Yingrui Zhang, Steven E. J. Bell & Yikai Xu

  2. Key Laboratory for Advanced Materials, Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, School of Chemistry and Molecular Engineering, East China University of Science & Technology, Shanghai, China

    Ziwei Ye

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Contributions

Conceptualization, Y.X., S.E.J.B., C.L. and Z.Y.; investigation, C.L., Y.Z. and Y.X.; formal analysis, C.L., Y.X., S.E.J.B., Z.Y. and Y.Z.; writing—original draft, C.L. and Y.X.; writing—reviewing and editing, Y.X., C.L., S.E.J.B., Z.Y. and Y.Z.; supervision, Y.X. and S.E.J.B.; project administration, Y.X.; funding acquisition, S.E.J.B., Y.X. and Y.Z.

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Correspondence to Steven E. J. Bell or Yikai Xu.

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Key references using this protocol

Xu, Y. et al. Nano Lett. 16, 5255–5260 (2016): https://doi.org/10.1021/acs.nanolett.6b02418

Li, C. et al. Chem 8, 2514–2528 (2022): https://doi.org/10.1016/j.chempr.2022.06.008

Ye, Z. et al. JACS Au 2, 178–187 (2022): https://doi.org/10.1021/jacsau.1c00462

Extended data

Extended Data Fig. 1 The aggregation kinetics of CRGC monitored by SERS.

(a) Plot showing the intensity of the Au-Cl vibration band measured over time. (b) SERS spectra of aggregated CRGC obtained 30 seconds, 150 seconds, 300 seconds, 450 seconds, 600 seconds, 750 seconds and 900 seconds after adding in the aggregating agent.

Extended Data Fig. 2 SERS reproducibility data using aggregated colloid.

SERS data obtained from five independent samples of aggregated CRSC.

Extended Data Fig. 3 SEM images of nanoparticle-polymer films formed with incorrect particle concentrations.

(a) A typical CRGC nanoparticle-polymer film formed with low concentrations of particles leading to a loosely packed particle layer. (b) A typical CRGC nanoparticle-polymer film formed with high concentrations of particles leading to the formation of wrinkles in the particle layer. Scale bars, 500 nm.

Extended Data Fig. 4 Optical microscopy image showing a MeLLF sample before and after being damaged by laser irradiation.

(a) A CRSC MeLLF observed with a confocal Raman microscope. (b) The same area of the MeLLF after being damaged with laser irradiation. Scale bars, 100 µm.

Supplementary information

Reporting Summary

Supplementary Video 1

Procedure for making a CRGC nanoparticle–polymer film.

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Li, C., Zhang, Y., Ye, Z. et al. Combining surface-accessible Ag and Au colloidal nanomaterials with SERS for in situ analysis of molecule–metal interactions in complex solution environments. Nat Protoc 18, 2717–2744 (2023). https://doi.org/10.1038/s41596-023-00851-6

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  • DOI: https://doi.org/10.1038/s41596-023-00851-6

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