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Nanoparticle surfactants for kinetically arrested photoactive assemblies to track light-induced electron transfer

Nature Nanotechnology volume 16, pages 1121–1129 (2021)Cite this article

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Abstract

Nature controls the assembly of complex architectures through self-limiting processes; however, few artificial strategies to mimic these processes have been reported to date. Here we demonstrate a system comprising two types of nanocrystal (NC), where the self-limiting assembly of one NC component controls the aggregation of the other. Our strategy uses semiconducting InP/ZnS core–shell NCs (3 nm) as effective assembly modulators and functional nanoparticle surfactants in cucurbit[n]uril-triggered aggregation of AuNCs (5–60 nm), allowing the rapid formation (within seconds) of colloidally stable hybrid aggregates. The resultant assemblies efficiently harvest light within the semiconductor substructures, inducing out-of-equilibrium electron transfer processes, which can now be simultaneously monitored through the incorporated surface-enhanced Raman spectroscopy–active plasmonic compartments. Spatial confinement of electron mediators (for example, methyl viologen (MV2+)) within the hybrids enables the direct observation of photogenerated radical species as well as molecular recognition in real time, providing experimental evidence for the formation of elusive σ–(MV+)2 dimeric species. This approach paves the way for widespread use of analogous hybrids for the long-term real-time tracking of interfacial charge transfer processes, such as the light-driven generation of radicals and catalysis with operando spectroscopies under irreversible conditions.

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Fig. 1: Self-limiting assembly processes.
Fig. 2: Schematic of ISLA-assisted self-assembly processes of semiconductor/metal hybrids.
Fig. 3: Self-limiting self-assembly of InP/ZnS NCs and CB[7].
Fig. 4: Overview of kinetic arrest of plasmonic assemblies through ISLA and the formation of hybrid systems.
Fig. 5: Tracking light-driven out-of-equilibrium redox chemistry within hybrid aggregates.
Fig. 6: Real-time monitoring of light-induced redox-driven molecular recognition processes.

Data availability

Methods and materials characterization are provided in the Supplementary Information. The data that support the findings of this study are available from the corresponding author on reasonable request.

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Acknowledgements

We acknowledge financial support from EPSRC grant nos. EP/L027151/1 (NOtCH) and EP/R020965/1 (RaNT). J.H. is thankful for support from the Chinese Scholarship Council and Cambridge Commonwealth, European and International Trust. B.d.N. acknowledges support from the Leverhulme Trust and Isaac Newton Trust. R.C. acknowledges support from Trinity College, Cambridge. S.M.C. thanks Girton College, Cambridge, for a Henslow Research Fellowship. We thank S. J. Barrow, A. S. Groombridge and I. Szabó for helpful discussions. We acknowledge use of the research computing facility at King’s College London, Rosalind (https://rosalind.kcl.ac.uk).

Author information

Author notes

  1. These authors contributed equally: Kamil Sokołowski, Junyang Huang.

Authors and Affiliations

  1. Melville Laboratory for Polymer Synthesis, Yusuf Hamied Department of Chemistry, University of Cambridge, Cambridge, UK

    Kamil Sokołowski, Jade A. McCune, David D. Xu & Oren A. Scherman

  2. Institute of Physical Chemistry, Polish Academy of Science, Warsaw, Poland

    Kamil Sokołowski

  3. NanoPhotonics Centre, Cavendish Laboratory, University of Cambridge, Cambridge, UK

    Junyang Huang, Bart de Nijs, Rohit Chikkaraddy & Jeremy J. Baumberg

  4. Department of Chemistry, King’s College London, London, UK

    Tamás Földes & Edina Rosta

  5. Department of Materials Science and Metallurgy, University of Cambridge, Cambridge, UK

    Sean M. Collins

  6. Department of Physics and Astronomy, University College London, Gower Street, UK

    Tamás Földes & Edina Rosta

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Contributions

K.S. and O.A.S. conceived the project and developed the experiments. K.S. developed and prepared the materials. K.S. and J.A.M. carried out the mechanistic studies on self-limiting aggregation. K.S. and O.A.S. proposed the aggregation mechanism. D.D.X. carried out the zeta potential measurements. K.S. and J.H. carried out SERS experiments. K.S., J.H., B.d.N. and J.J.B. analysed the SERS data while K.S. and O.A.S. provided interpretation and proposed a mechanism for the photochemical transformations. T.F. and E.R. carried out the theoretical calculations. K.S. and S.M.C. carried out TEM experiments. R.C. carried out calculations on the optical properties of AuNC aggregates while R.C., J.H., B.d.N. and J.J.B. provided their interpretation. K.S., J.A.M. and O.A.S. analysed the data and wrote the manuscript with input from all co-authors.

Corresponding author

Correspondence to Oren A. Scherman.

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The authors declare no competing interests.

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Peer review information Nature Nanotechnology thanks Hongyu Chen, Zhihong Nie and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary information

Supplementary Figs. 1–47, Table 1, discussion, materials and methods, and coordinates for the optimized structure.

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Sokołowski, K., Huang, J., Földes, T. et al. Nanoparticle surfactants for kinetically arrested photoactive assemblies to track light-induced electron transfer. Nat. Nanotechnol. 16, 1121–1129 (2021). https://doi.org/10.1038/s41565-021-00949-6

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