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Atomically precise photothermal nanomachines

Nature Materials (2023)Cite this article

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Abstract

Interfacing molecular machines to inorganic nanoparticles can, in principle, lead to hybrid nanomachines with extended functions. Here we demonstrate a ligand engineering approach to develop atomically precise hybrid nanomachines by interfacing gold nanoclusters with tetraphenylethylene molecular rotors. When gold nanoclusters are irradiated with near-infrared light, the rotation of surface-decorated tetraphenylethylene moieties actively dissipates the absorbed energy to sustain the photothermal nanomachine with an intact structure and steady efficiency. Solid-state nuclear magnetic resonance and femtosecond transient absorption spectroscopy reveal that the photogenerated hot electrons are rapidly cooled down within picoseconds via electron–phonon coupling in the nanomachine. We find that the nanomachine remains structurally and functionally intact in mammalian cells and in vivo. A single dose of near-infrared irradiation can effectively ablate tumours without recurrence in tumour-bearing mice, which shows promise in the development of nanomachine-based theranostics.

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Fig. 1: Design and characterization of an atomically precise PTG nanomachine with sustained photothermal conversion.
Fig. 2: Structural analysis of the interfacial interactions in the ligand monolayer of the atomically precise nanomachine.
Fig. 3: Rotation ability of the PTG nanomachine and its structural intactness under NIR irradiation.
Fig. 4: Operation of the PTG nanomachine under different working conditions.
Fig. 5: Photothermal conversion efficiency, pharmacokinetic profile and biodistribution of PTG NPs in mice.
Fig. 6: Efficacy of PTG-NP-based PTT treatment of tumours.

Data availability

All data supporting the findings in this study are available within the Article and its Supplementary Information. Raw data of all the histology images are available via Figshare at https://figshare.com/s/83838f30afc8b88da550. The crystallographic data for the structures reported in this Article have been deposited at the Cambridge Crystallographic Data Centre, under deposition number CCDC 2286681. Additional raw data generated in this study are available from the corresponding authors upon request. Source data are provided with this paper.

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Acknowledgements

We thank W. Xu for help with the NMR data analysis. This work was financially supported by the National Key R&D Program of China (2020YFA0908104, to J.S.), the National Natural Science Foundation of China (21904087, to J.S.; 21834007, to C.F.; 21991134, to C.F.; 91953106, to J.S.; 21934007 and 92056117, to X.L.; 22022410, to Y. Zhu; 82050005, to Y. Zhu; T2188102, to C.F.), the Shanghai Municipal Science and Technology Commission (21QA1404800, to J.S.; 22JC1401203, to Y. Zhu; 20dz1101000 and 20dz1101001, to C.F.; 20dz1101002, to J.S.), Shenzhen Key Laboratory of Functional Aggregate Materials (ZDSYS20211021111400001, to B.Z.T), the Science Technology Innovation Commission of Shenzhen Municipality (KQTD20210811090142053, to B.Z.T) and the New Cornerstone Science Foundation (to C.F.).

Author information

Author notes

  1. These authors contributed equally: Jing Chen, Peilin Gu, Guangliu Ran, Yu Zhang.

Authors and Affiliations

  1. Institute of Materiobiology, Department of Chemistry, College of Science, Shanghai University, Shanghai, China

    Jing Chen, Jiang Li, Lihua Wang & Ying Zhu

  2. The Interdisciplinary Research Center, Shanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, China

    Jing Chen, Yu Zhang & Rui Sun

  3. Division of Physical Biology, CAS Key Laboratory of Interfacial Physics and Technology, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, China

    Peilin Gu & Xiaobin Fu

  4. University of Chinese Academy of Sciences, Beijing, China

    Peilin Gu

  5. Department of Physics and Applied Optics Beijing Area Major Laboratory, Center for Advanced Quantum Studies, Beijing Normal University, Beijing, China

    Guangliu Ran & Wenkai Zhang

  6. School of Chemistry and Chemical Engineering, New Cornerstone Science Laboratory, Frontiers Science Center for Transformative Molecules, Zhangjiang Institute for Advanced Study and National Center for Translational Medicine, Shanghai Jiao Tong University, Shanghai, China

    Mingqiang Li, Xiaoguo Liu, Jianlei Shen & Chunhai Fan

  7. School of Material Science and Chemical Engineering, Ningbo University, Ningbo, China

    Bin Chen

  8. Zhangjiang Laboratory, Shanghai, China

    Hui Lu & Lihua Wang

  9. State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China

    Ying-Zi Han & Zichao Tang

  10. Xiangfu Laboratory, Jiashan, China

    Qinglong Yan & Rui Sun

  11. Key Laboratory of Artificial Structures and Quantum Control (Ministry of Education), Shenyang National Laboratory for Materials Science, School of Physics and Astronomy, Shanghai Jiao Tong University, Shanghai, China

    Guorui Chen, Zhiwen Shi & Shiyong Wang

  12. School of Science and Engineering, Shenzhen Institute of Aggregate Science and Technology, The Chinese University of Hong Kong, Shenzhen, China

    Ben Zhong Tang

  13. Institute of Molecular Medicine, Shanghai Key Laboratory for Nucleic Acids Chemistry and Nanomedicine, Renji Hospital, School of Medicine, Shanghai Jiao Tong University, Shanghai, China

    Chunhai Fan

Authors
  1. Jing Chen
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Contributions

J.C. performed the synthesis of nanoclusters and analysed the spectroscopy results. P.G., Y. Zhang, Y. Zhu, Q.Y. and R.S. performed all the photothermal conversion and PTT experiments. B.C. and H.L. synthesized the alkynyl TPE. G.R. and W.Z. performed the transient absorption measurements. Y.-Z.H. and Z.T. performed the mass spectroscopy measurement. X.F. performed the NMR measurements. M.L., G.C., Z.S. and S.W. provided technical assistance on the NMR and transient absorption spectra studies. Y. Zhu, Y. Zhang, X.L., J.L. and L.W. technically assisted in the in vitro and in vivo experiments. J.S., B.Z.T. and C.F. conceived the project idea. Y. Zhu, J.S. and C.F. wrote the manuscript. J.S. and C.F. directed the project.

Corresponding authors

Correspondence to Ying Zhu, Jianlei Shen, Ben Zhong Tang or Chunhai Fan.

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Nature Materials thanks Samuel Achilefu, James Tour and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Source Data Fig. 4

Statistical source data and unprocessed TEM and SEM images.

Source Data Fig. 5

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Source Data Fig. 6

Statistical source data.

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Chen, J., Gu, P., Ran, G. et al. Atomically precise photothermal nanomachines. Nat. Mater. (2023). https://doi.org/10.1038/s41563-023-01721-y

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