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Symmetry-breaking in patch formation on triangular gold nanoparticles by asymmetric polymer grafting

Author

Listed:
  • Ahyoung Kim

    (University of Illinois)

  • Thi Vo

    (University of Michigan)

  • Hyosung An

    (University of Illinois
    Chonnam National University)

  • Progna Banerjee

    (Argonne National Laboratory
    The University of Texas at Austin)

  • Lehan Yao

    (University of Illinois)

  • Shan Zhou

    (University of Illinois
    South Dakota School of Mines and Technology)

  • Chansong Kim

    (University of Illinois)

  • Delia J. Milliron

    (Argonne National Laboratory)

  • Sharon C. Glotzer

    (University of Michigan
    University of Michigan)

  • Qian Chen

    (University of Illinois
    University of Illinois
    University of Illinois
    University of Illinois)

Abstract

Synthesizing patchy particles with predictive control over patch size, shape, placement and number has been highly sought-after for nanoparticle assembly research, but is fraught with challenges. Here we show that polymers can be designed to selectively adsorb onto nanoparticle surfaces already partially coated by other chains to drive the formation of patchy nanoparticles with broken symmetry. In our model system of triangular gold nanoparticles and polystyrene-b-polyacrylic acid patch, single- and double-patch nanoparticles are produced at high yield. These asymmetric single-patch nanoparticles are shown to assemble into self-limited patch‒patch connected bowties exhibiting intriguing plasmonic properties. To unveil the mechanism of symmetry-breaking patch formation, we develop a theory that accurately predicts our experimental observations at all scales—from patch patterning on nanoparticles, to the size/shape of the patches, to the particle assemblies driven by patch‒patch interactions. Both the experimental strategy and theoretical prediction extend to nanoparticles of other shapes such as octahedra and bipyramids. Our work provides an approach to leverage polymer interactions with nanoscale curved surfaces for asymmetric grafting in nanomaterials engineering.

Suggested Citation

  • Ahyoung Kim & Thi Vo & Hyosung An & Progna Banerjee & Lehan Yao & Shan Zhou & Chansong Kim & Delia J. Milliron & Sharon C. Glotzer & Qian Chen, 2022. "Symmetry-breaking in patch formation on triangular gold nanoparticles by asymmetric polymer grafting," Nature Communications, Nature, vol. 13(1), pages 1-14, December.
  • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-34246-0
    DOI: 10.1038/s41467-022-34246-0
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    References listed on IDEAS

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    1. Zhenxing Wang & Bowen He & Gefei Xu & Guojing Wang & Jiayi Wang & Yuhua Feng & Dongmeng Su & Bo Chen & Hai Li & Zhonghua Wu & Hua Zhang & Lu Shao & Hongyu Chen, 2018. "Transformable masks for colloidal nanosynthesis," Nature Communications, Nature, vol. 9(1), pages 1-9, December.
    2. Binbin Luo & Ahyoung Kim & John W. Smith & Zihao Ou & Zixuan Wu & Juyeong Kim & Qian Chen, 2019. "Hierarchical self-assembly of 3D lattices from polydisperse anisometric colloids," Nature Communications, Nature, vol. 10(1), pages 1-9, December.
    3. Qian Chen & Sung Chul Bae & Steve Granick, 2011. "Directed self-assembly of a colloidal kagome lattice," Nature, Nature, vol. 469(7330), pages 381-384, January.
    4. Jung-Hoon Lee & Kyle J. Gibson & Gang Chen & Yossi Weizmann, 2015. "Bipyramid-templated synthesis of monodisperse anisotropic gold nanocrystals," Nature Communications, Nature, vol. 6(1), pages 1-9, November.
    5. Rachelle M. Choueiri & Elizabeth Galati & Héloïse Thérien-Aubin & Anna Klinkova & Egor M. Larin & Ana Querejeta-Fernández & Lili Han & Huolin L. Xin & Oleg Gang & Ekaterina B. Zhulina & Michael Rubins, 2016. "Surface patterning of nanoparticles with polymer patches," Nature, Nature, vol. 538(7623), pages 79-83, October.
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