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Chiral templating of self-assembling nanostructures by circularly polarized light

Nature Materials volume 14, pages 66–72 (2015)Cite this article

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Abstract

The high optical and chemical activity of nanoparticles (NPs) signifies the possibility of converting the spin angular momenta of photons into structural changes in matter. Here, we demonstrate that illumination of dispersions of racemic CdTe NPs with right- (left-)handed circularly polarized light (CPL) induces the formation of right- (left-)handed twisted nanoribbons with an enantiomeric excess exceeding 30%, which is ∼10 times higher than that of typical CPL-induced reactions. Linearly polarized light or dark conditions led instead to straight nanoribbons. CPL ‘templating’ of NP assemblies is based on the enantio-selective photoactivation of chiral NPs and clusters, followed by their photooxidation and self-assembly into nanoribbons with specific helicity as a result of chirality-sensitive interactions between the NPs. The ability of NPs to retain the polarization information of incident photons should open pathways for the synthesis of chiral photonic materials and allow a better understanding of the origins of biomolecular homochirality.

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Figure 1: Self-assembly of CdTe NPs into twisted nanoribbons induced by illumination with CPL.
Figure 2: Chirality of single nanoribbons.
Figure 3: Mechanism of enantio-selective assembly of NPs.
Figure 4: Molecular dynamics and experimental studies of the self-assembly of chiral NPs.

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Acknowledgements

This material is based on work partially supported by the Center for Solar and Thermal Energy Conversion, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under award number #DE-SC0000957, and by ARO MURI W911NF-12-1-0407 ‘Coherent Effects in Hybrid Nanostructures for Lineshape Engineering of Electromagnetic Media’ (N.A.K. and S.L.). We acknowledge support from the NSF under grant ECS-0601345; CBET 0933384; CBET 0932823; and CBET 1036672. Financial support from the Robert A. Welch Foundation (C-1664) is also acknowledged (S.L.). Support from the NIH grant GM085043 (P.Z.) is gratefully acknowledged. The work of P.K. was supported by the NSF DMR grant No. 1309765 and by the ACS PRF grant No. 53062-ND6. The authors thank J-Y. Kim for assistance with chiral NP assembly experiments.

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Authors and Affiliations

  1. Department of Macromolecular Science and Engineering, University of Michigan, Ann Arbor, Michigan 48109, USA

    Jihyeon Yeom & Nicholas A. Kotov

  2. Department of Chemical Engineering, University of Michigan, Ann Arbor, Michigan 48109, USA

    Bongjun Yeom & Nicholas A. Kotov

  3. Department of Chemistry, University of Illinois at Chicago, Chicago, Illinois 60607, USA

    Henry Chan & Petr Král

  4. Department of Chemistry, Rice University, Houston, Texas 77005, USA

    Kyle W. Smith, Sergio Dominguez-Medina, Wei-Shun Chang & Stephan Link

  5. Department of Biomedical Engineering, University of Michigan, Ann Arbor, Michigan 48109, USA

    Joong Hwan Bahng & Nicholas A. Kotov

  6. Department of Structural Biology, University of Pittsburgh School of Medicine, Pittsburgh, Pennsylvania 15260, USA

    Gongpu Zhao & Peijun Zhang

  7. Division of Material Sciences, Korea Basic Science Institute, Daejeon 305-333, Republic of Korea

    Sung-Jin Chang

  8. Department of Chemistry, Chung-Ang University, 84 Heukseok-ro Dongjak-gu 156-756, Republic of Korea,

    Sung-Jin Chang

  9. CIC NanoGUNE Consolider, Tolosa Hiribidea 76, Donostia-San Sebastian 20018, Spain

    Andrey Chuvilin & Dzmitry Melnikau

  10. Ikerbasque, Basque Foundation for Science, Alameda Urquijo 36-5, 48011 Bilbao, Spain

    Andrey Chuvilin

  11. Centro de Física de Materiales (MPC, CSIC-UPV/EHU), Po Manuel de Lardizabal 5, Donostia-San Sebastian 20018, Spain

    Dzmitry Melnikau

  12. Department of Physics and Materials Science and Centre for Functional Photonics (CFP); City University of Hong Kong, 83 Tat Chee Avenue Kowloon, Hong Kong,

    Andrey L. Rogach

  13. City University of Hong Kong, 83 Tat Chee Avenue Kowloon, Hong Kong,

    Andrey L. Rogach

  14. Department of Mechanical Engineering and Materials Science, Swanson School of Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, USA

    Peijun Zhang

  15. Department of Physics, University of Illinois at Chicago, Chicago, Illinois 60607, USA

    Petr Král

Authors
  1. Jihyeon Yeom
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Contributions

N.A.K. conceived the project. J.Y. built the experimental set-up and performed the experiments. B.Y. carried out ME-FEM simulations. H.C. and P.K. undertook atomistic MD simulations. K.W.S., S.D-M., W-S.C. and S.L. measured CD signals from a single nanoribbon. J.H.B. conducted E-DLVO calculations and synthesis of L- and D-cysteine-stabilized CdTe nanostructures. G.Z. and P.Z. carried out 3D TEM tomography. S-J.C. conducted AFM measurements. A.C., D.M. and A.L.R. measured high-resolution HAADF and TEM images of truncated tetrahedral CdTe NPs. J.Y., B.Y. and N.A.K. analysed data. J.Y. and N.A.K. wrote the manuscript.

Corresponding author

Correspondence to Nicholas A. Kotov.

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The authors declare no competing financial interests.

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Yeom, J., Yeom, B., Chan, H. et al. Chiral templating of self-assembling nanostructures by circularly polarized light. Nature Mater 14, 66–72 (2015). https://doi.org/10.1038/nmat4125

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