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Direct visualization of ligands on gold nanoparticles in a liquid environment

Nature Chemistry (2024)Cite this article

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Abstract

The interactions between gold nanoparticles, their surface ligands and the solvent critically influence the properties of these nanoparticles. Although spectroscopic and scattering techniques have been used to investigate their ensemble structure, a comprehensive understanding of these processes at the nanoscale remains challenging. Electron microscopy makes it possible to characterize the local structure and composition but is limited by insufficient contrast, electron beam sensitivity and the requirement for ultrahigh-vacuum conditions, which prevent the investigation of dynamic aspects. Here we show that, by exploiting high-quality graphene liquid cells, we can overcome these limitations and investigate the structure of the ligand shell around gold nanoparticles and at the ligand–gold interface in a liquid environment. Using this graphene liquid cell, we visualize the anisotropy, composition and dynamics of ligand distribution on gold nanorod surfaces. Our results indicate a micellar model for surfactant organization. This work provides a reliable and direct visualization of ligand distribution around colloidal nanoparticles.

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Fig. 1: Comparison of TEM investigation of gold NRs capped with CTAB ligands in dried state on a graphene grid and in a liquid environment.
Fig. 2: AC-HRTEM images of different gold NRs capped with CTAB ligands in a liquid environment.
Fig. 3: Dynamic motion of a CTAB micelle in a GLC.
Fig. 4: EDX-STEM analysis of a CTAB-capped gold NR encapsulated in a graphene GLC.

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All data supporting the findings of this study are included in the Article, Supplementary Information and source data files. Source data are provided with this paper.

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Acknowledgements

S.B. and A.P.-T. acknowledge financial support from the European Commission under the Horizon 2020 Programme by grant number 731019 (EUSMI) and ERC Consolidator grant number 815128 (REALNANO). D.W. acknowledges an Individual Fellowship funded by the Marie Sklodowska-Curie Actions (MSCA) in Horizon 2020 programme (grant 894254 SuprAtom). L.M.L.-M. acknowledges financial support from the European Research Council (ERC Advanced Grant 787510, 4DbioSERS) and the Spanish State Research Agency (Project PID2020-117779RB-I00 and MDM-2017-0720). The authors acknowledge J. Mosquera and D. Jimenez de Aberasturi for provision of samples and useful discussions.

Author information

Author notes

  1. These authors contributed equally: Adrián Pedrazo-Tardajos, Nathalie Claes, Da Wang.

Authors and Affiliations

  1. EMAT-University of Antwerp, Antwerp, Belgium

    Adrián Pedrazo-Tardajos, Nathalie Claes, Da Wang, Proloy Nandi, Kellie Jenkinson, Robin De Meyer & Sara Bals

  2. NANOlab Center of Excellence, University of Antwerp, Antwerp, Belgium

    Adrián Pedrazo-Tardajos, Nathalie Claes, Da Wang, Proloy Nandi, Kellie Jenkinson, Robin De Meyer & Sara Bals

  3. CIC biomaGUNE, Donostia-San Sebastián, Spain

    Ana Sánchez-Iglesias & Luis M. Liz-Marzán

  4. Centro de Investigación Biomédica en Red, Bioingeniería, Biomateriales y Nanomedicina, CIBER-BBN, Donostia-San Sebastián, Spain

    Ana Sánchez-Iglesias & Luis M. Liz-Marzán

  5. Ikerbasque, Basque Foundation for Science, Bilbao, Spain

    Luis M. Liz-Marzán

  6. Cinbio, Universidade de Vigo, Vigo, Spain

    Luis M. Liz-Marzán

Authors
  1. Adrián Pedrazo-Tardajos
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Contributions

A.P.-T., L.M.L.-M. and S.B. conceived the project. A.S.-I. prepared the samples and performed initial characterization. A.P.-T., N.C., D.W., P.N., K.J. and R.D.M. performed all TEM investigations and further analysis. A.P.-T., N.C., D.W., L.M.L.-M. and S.B. wrote the paper with comments from all authors.

Corresponding author

Correspondence to Sara Bals.

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Extended data

Extended Data Fig. 1 Aberration corrected high resolution TEM (AC-HRTEM) images of different graphene TEM grids.

a) Commercial graphene grid and b) the optimized home-made graphene grid. The insets show the corresponding Fourier transformations. The Fourier transformation of the commercial grid (a) demonstrates a diffuse diffraction pattern that is typical of amorphous features, whereas the Fourier transformation of the optimized graphene grid (b) shows more clear spots indicating a clean graphene lattice.

Extended Data Fig. 2 Visualization of PEG-SH capped Au NRs in different environments.

a-c) Schematic illustrations and d-f) AC-HRTEM images of a Au NRs capped with PEG-SH d) dried on a graphene grid under an ambient environment e) encapsulated in a GLC containing a relatively thick liquid layer and f) encapsulated in a GLC containing a relatively thin liquid layer.

Extended Data Fig. 3 Thickness of PEG-SH ligands layer in GLC, where thin layer of liquid was present.

a) A representative AC-HRTEM image denoting the measured areas on the tips and sides of a single SC Au NR in a thin liquid cell. b) Corresponding ligand shell thickness at tips and sides is 2.84 ± 0.10 nm and 6.65 ± 0.21 nm, respectively. Note that the histogram was plotted by measuring multiple Au NRs in the GLC.

Supplementary information

Supplementary Information

Supplementary Figs. 1–17 and Tables 1–4.

Supplementary Video 1

Video of a Au NR encapsulated in a GLC. The motion of Au NRs and the formation of bubbles are indicated by the yellow arrow and prove the presence of liquid in the GLC.

Supplementary Video 2

Video of a micellar structure next to the Au nanorod. The movement of the micellar structure in the GLC is tracked and indicated by the yellow ellipse.

Source data

Source Data Fig. 1

Data histograms.

Source Data Fig. 4

Data line profiles.

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Pedrazo-Tardajos, A., Claes, N., Wang, D. et al. Direct visualization of ligands on gold nanoparticles in a liquid environment. Nat. Chem. (2024). https://doi.org/10.1038/s41557-024-01574-1

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