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Dynamic hook-and-eye nanoparticle sponges

Nature Chemistry volume 1, pages 733–738 (2009)Cite this article

Abstract

Systems in which nanoscale components of different types can be captured and/or released from organic scaffolds provide a fertile basis for the construction of dynamic, exchangeable functional materials. In such heterogeneous systems, the components interact with one another by means of programmable, noncovalent bonding interactions. Herein, we describe polymers that capture and release functionalized nanoparticles selectively during redox-controlled aggregation and disaggregation, respectively. The interactions between the polymer and the NPs are mediated by the reversible formation of polypseudorotaxanes, and give rise to architectures ranging from short chains composed of few nanoparticles to extended networks of nanoparticles crosslinked by the polymer. In the latter case, the polymer/nanoparticle aggregates precipitate from solution such that the polymer acts as a selective ‘sponge’ for the capture/release of the nanoparticles of different types.

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Figure 1: Complexation of electron-rich nanoparticles with an electron-deficient polymer.
Figure 2: The polymer/nanoparticle ratio affects the morphology of the resulting complex.
Figure 3: Hierarchical assembly of nanoparticle/polymer complexes.
Figure 4: Reversible binding of TTF-functionalized NPs to 14n+.
Figure 5: Hook-and-eye sorting of nanoparticles.

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Acknowledgements

The research was supported by the Microelectronics Advanced Research Corporation and its Focus Center of Functional Engineered NanoArchitectonics. B.A.G. gratefully acknowledges the financial support from the Alfred P. Sloan Fellowship and from The Dreyfus Teacher-Scholar Award. Development of theoretical models was supported by the Non-equilibrium Energy Research Center an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under award number DE-SC0000989. R.K. was supported by the NSF under the Northwestern MRSEC. L.F. gratefully acknowledges the support of the Ryan Fellowship at Northwestern University.

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Authors and Affiliations

  1. Department of Chemical and Biological Engineering,

    Rafal Klajn, Paul J. Wesson, Siowling Soh & Bartosz A. Grzybowski

  2. Department of Chemistry, Northwestern University, 2145 Sheridan Rd, Evanston, 60208, Illinois, USA

    Rafal Klajn, Mark A. Olson, Lei Fang, Ali Coskun, Ali Trabolsi, J. Fraser Stoddart & Bartosz A. Grzybowski

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Contributions

B.A.G. and J.F.S. conceived the project and prepared the manuscript. M.A.O. synthesized polymer 14n+. L.F., A.C. and M.A.O. synthesized dithiolane ligands for nanoparticles. R.K. synthesized and functionalized nanoparticles and prepared nanoparticle–polymer complexes. P.J.W. and S.S. developed theoretical models. A.T. performed electrochemical experiments.

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Correspondence to J. Fraser Stoddart or Bartosz A. Grzybowski.

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Klajn, R., Olson, M., Wesson, P. et al. Dynamic hook-and-eye nanoparticle sponges. Nature Chem 1, 733–738 (2009). https://doi.org/10.1038/nchem.432

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