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Hollow nanotubular toroidal polymer microrings

Nature Chemistry volume 6, pages 97103 (2014) | Download Citation

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Abstract

Despite the remarkable progress made in the self-assembly of nano- and microscale architectures with well-defined sizes and shapes, a self-organization-based synthesis of hollow toroids has, so far, proved to be elusive. Here, we report the synthesis of polymer microrings made from rectangular, flat and rigid-core monomers with anisotropically predisposed alkene groups, which are crosslinked with each other by dithiol linkers using thiol-ene photopolymerization. The resulting hollow toroidal structures are shape-persistent and mechanically robust in solution. In addition, their size can be tuned by controlling the initial monomer concentrations, an observation that is supported by a theoretical analysis. These hollow microrings can encapsulate guest molecules in the intratoroidal nanospace, and their peripheries can act as templates for circular arrays of metal nanoparticles.

  • Compound C26H24O6

    2,3,6,7-Tetrakis(allyloxy)anthracene-9,10-dione

  • Compound C6H14O2S2

    3,6-Dioxa-1,8-octanedithiol

  • Compound C48H44N2O4

    N,N,N',N'-Tetrakis(4-allyloxyphenyl)biphenyl-4,4'-diamine

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Acknowledgements

This work was supported by the Institute for Basic Science (IBS; CA1303) and the World Class University Project (R31–2008–000–10059–0) in Korea. W.S. acknowledges support from the Korea Research Foundation (NRF-2013R1A1A2008900) and the Brain–Korea 21 Program. C.G.P. acknowledges support from POSCO through the Korean Steel NanoFusion Program. The authors thank J.M. Kim, Z. Hassan and D. Shetty for discussions.

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Affiliations

  1. Center for Self-assembly and Complexity, Institute for Basic Science (IBS), Pohang, 790–784, Republic of Korea

    • Jiyeong Lee
    • , Kangkyun Baek
    • , Gyeongwon Yun
    • , Young Ho Ko
    • , Ilha Hwang
    • , Jeehong Kim
    •  & Kimoon Kim
  2. Department of Chemistry, Pohang University of Science and Technology, Pohang, 790–784, Republic of Korea

    • Jiyeong Lee
    • , Kangkyun Baek
    • , Gyeongwon Yun
    • , Ilha Hwang
    • , Jeehong Kim
    •  & Kimoon Kim
  3. Department of Physics, Pohang University of Science and Technology, Pohang, 790–784, Republic of Korea

    • Myungjin Kim
    •  & Wokyung Sung
  4. National Institute for Nanomaterials Technology, Pohang University of Science and Technology, Pohang, 790–784, Republic of Korea

    • Nam-Suk Lee
    •  & Chan Gyung Park
  5. Division of Advanced Materials Science, Pohang University of Science and Technology, Pohang, 790–784, Republic of Korea

    • Ramalingam Natarajan
    •  & Kimoon Kim
  6. Department of Materials Science and Engineering, Pohang University of Science and Technology, Pohang, 790-784, Republic of Korea

    • Chan Gyung Park

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Contributions

K.K. and J.L. conceived and designed the project. J.L. carried out most of the experimental work. K.B. and R.N. provided invaluable guidance. Y.H.K. provided expertise with NMR analysis. G.Y., N.L. and C.G.P. performed the TEM experiments. M.K. and W.S. performed theoretical studies of the formation of the microrings. K.K., W.S., R.N., K.B. and J.L. wrote the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding authors

Correspondence to Wokyung Sung or Kimoon Kim.

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DOI

https://doi.org/10.1038/nchem.1833