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Self-assembly of metal–polymer analogues of amphiphilic triblock copolymers

Nature Materials volume 6, pages 609–614 (2007)Cite this article

Abstract

Organized arrays of anisotropic nanoparticles show electronic and optical properties that originate from the coupling of shape-dependent properties of the individual nanorods. The organization of nanorods in a controllable and predictable way provides a route to the fabrication of new materials and functional devices. So far, significant progress has been achieved in the self-assembly of nanorod arrays, yet the realization of a range of different structures requires changing the surface chemistry of the nanoparticles. We organized metal nanorods in structures with varying geometries by using a striking analogy between amphiphilic ABA triblock copolymers and the hydrophilic nanorods tethered with hydrophobic polymer chains at both ends. The self-assembly was tuneable and reversible and it was achieved solely by changing the solvent quality for the constituent blocks. This approach provides a new route to the organization of anisotropic nanoparticles by using the strategies that are established for the self-assembly of block copolymers.

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Figure 1: Self-assembly of polymer-tethered gold nanorods in selective solvents.
Figure 2: Formation of rings of triblocks in DMF/water mixtures.
Figure 3: Formation of linear chains in DMF/water mixture.
Figure 4: Absorption spectra of the linear nanochains.
Figure 5: Formation of nanospheres in the THF/water mixture.

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Acknowledgements

E.K. is grateful for Canada Research Chair financial support (NSERC Canada). G.C.W. gratefully acknowledges NSERC Canada (grant 312497), NSF (grant CHE-0404579), ONR (grant N00014-05-10765), ARO (grant W911NF-04-1-0191) and NIH (grant 1 R21 EB003101-01) for financially supporting this work. M.R. acknowledges financial support from NSF (grants CHE-0616925 and CTS-0609087), NIH (grant 1-R01-HL0775486A) and NASA (agreement NCC-1-02037). The authors thank Y. Wang for assistance in the synthesis of thiol-terminated polystyrene and D. Shirvanyants for assistance in image analysis.

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Authors and Affiliations

  1. Department of Chemistry, University of Toronto, 80 St George Street, Toronto, Ontario M5S 3H6, Canada

    Zhihong Nie, Daniele Fava, Eugenia Kumacheva, Shan Zou & Gilbert C. Walker

  2. Department of Chemical Engineering and Applied Chemistry, University of Toronto, 200 College Street, Toronto, Ontario M5S 3E5, Canada

    Eugenia Kumacheva

  3. Institute of Biomaterials & Biomedical Engineering, University of Toronto, 4 Taddle Creek Road, Toronto, Ontario M5S 3G9, Canada

    Eugenia Kumacheva

  4. Department of Chemistry, University of North Carolina, Chapel Hill, North Carolina 27599-3290, USA

    Michael Rubinstein

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  1. Zhihong Nie
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Contributions

Z.N. was responsible for project planning, data analysis and experimental work, D.F. was responsible for experimental work, S.Z. was responsible for experimental work and data analysis, G.C.W. and M.R. were responsible for data analysis and interpretation and E.K. was responsible for project planning and data analysis and interpretation.

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Correspondence to Eugenia Kumacheva.

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Nie, Z., Fava, D., Kumacheva, E. et al. Self-assembly of metal–polymer analogues of amphiphilic triblock copolymers. Nature Mater 6, 609–614 (2007). https://doi.org/10.1038/nmat1954

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