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Robust gold nanorods stabilized by bidentate N-heterocyclic-carbene–thiolate ligands

Nature Chemistry volume 11, pages 57–63 (2019)Cite this article

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Abstract

Although N-heterocyclic carbenes (NHCs) have demonstrated outstanding potential for use as surface anchors, synthetic challenges have limited their application to either large planar substrates or very small spherical nanoparticles. The development of a strategy to graft NHCs onto non-spherical nanomaterials, such as gold nanorods, would greatly expand their utility as surface ligands. Here, we use a bidentate thiolate–NHC–gold(i) complex that is easily grafted onto commercial cetyl trimethylammonium bromide-stabilized gold nanorods through ligand exchange. On mild reduction of the resulting surface-tethered NHC–gold(i) complexes, the gold atom attached to the NHC complex is added to the surface as an adatom, thereby precluding the need for reorganization of the underlying surface lattice upon NHC binding. The resulting thiolate–NHC-stabilized gold nanorods are stable towards excess glutathione for up to six days, and under conditions with large variations in pH, high and low temperatures, high salt concentrations, or in biological media and cell culture. We also demonstrate the utility of these nanorods for in vitro photothermal therapy.

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Fig. 1: Strategies for installation of NHCs onto gold nanomaterials.
Fig. 2: Synthesis and molecular characterization of PEGylated masked bidentate ligands.
Fig. 3: Installation of masked NHC–thiolate ligands onto commercial CTAB@Au nanorods.
Fig. 4: Characterization of NHC@Au-I.
Fig. 5: DFT calculations.
Fig. 6: Preliminary biological investigations using NHC@Au-I.

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Data availability

All data supporting the findings of this study are available within the Article and its Supplementary Information, and/or from the corresponding author upon reasonable request.

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Acknowledgements

The authors thank the National Science Foundation (CHE-1351646) for support of this work.

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Authors and Affiliations

  1. Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA, USA

    Michelle J. MacLeod, Aaron J. Goodman, Hong-Zhou Ye, Hung V.-T. Nguyen, Troy Van Voorhis & Jeremiah A. Johnson

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  1. Michelle J. MacLeod
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Contributions

M.J.M. and J.A.J. conceived the idea. M.J.M. conducted all synthesis and characterization studies. A.J.G. conducted laser irradiation experiments. H.Y. and T.V.V. conducted DFT calculations. H.V.-T.N. conducted cell culture assays. M.J.M. and J.A.J. wrote the manuscript. All authors read and revised the manuscript.

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Correspondence to Jeremiah A. Johnson.

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Detailed methods and materials, experimental protocols, characterization data (such as spectral data), Supplementary Figures 1–45 and Supplementary Table 1

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MacLeod, M.J., Goodman, A.J., Ye, HZ. et al. Robust gold nanorods stabilized by bidentate N-heterocyclic-carbene–thiolate ligands. Nature Chem 11, 57–63 (2019). https://doi.org/10.1038/s41557-018-0159-8

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