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Self-assembly of soft nanoparticles with tunable patchiness

Nature Nanotechnology volume 4, pages 721–726 (2009)Cite this article

Abstract

Details of the forces between nanoparticles determine the ways in which the nanoparticles can self-assemble into larger structures. The use of directed interactions has led to new concepts in self-assembly such as asymmetric dendrons1,2, Janus particles3, patchy colloids4,5,6 and colloidal molecules7. Recent models that include attractive regions or ‘patches’ on the surface of the nanoparticles predict a wealth of intricate modes of assembly8,9,10,11,12. Interactions between such particles are also important in a range of phenomena including protein aggregation13,14 and crystallization15, re-entrant phase transitions16,17,18, assembly of nanoemulsions19 and the organization of nanoparticles into nanowires20. Here, we report the synthesis of 6-nm nanoparticles with dynamic hydrophobic patches and show that they can form reversible self-assembled structures in aqueous solution that become topologically more connected upon dilution. The organization is based on guest–host supramolecular chemistry with the nanoparticles composed of a hydrophobic dendrimer host molecule and water-soluble hydrophilic guest molecules. The work demonstrates that subtle changes in hierarchal composition and/or concentration can dramatically change mesoscopic ordering.

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Figure 1: The molecular building blocks that make up the patchy nanoparticles and their assemblies.
Figure 2: Translational diffusion coefficients measured by 1H-DOSY NMR (in D2O, left axis) and shear viscosity measurements (in H2O, right axis).
Figure 3: 200 kV cryo-electron projection images of the patchy particles.
Figure 4: Analysing the reversible networks by determining their fractal dimension.
Figure 5: Light-scattering experiments performed on the reversible networks of patchy nanoparticles.

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Acknowledgements

The authors thank BSIK project 03033 and the Netherlands Organization for Scientific Research for financial support.

Author information

Authors and Affiliations

  1. Institute for Complex Molecular Systems, Eindhoven University of Technology, PO Box 513, Eindhoven, 5600, MB, The Netherlands

    Thomas M. Hermans, Marcel H. P. van Genderen & E. W. Meijer

  2. Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, PO Box 513, Eindhoven, 5600, MB, The Netherlands

    Thomas M. Hermans, Maarten A. C. Broeren, Marcel H. P. van Genderen & E. W. Meijer

  3. Department of Materials Science and Technology, University of Crete and F.O.R.T.H., PO Box 1527, Heraklion, 71110, Greece

    Nikos Gomopoulos & George Fytas

  4. Group Theory of Polymers and Soft Matter, Eindhoven University of Technology, PO Box 513, Eindhoven, 5600, MB, The Netherlands

    Paul van der Schoot

  5. Soft Matter CryoTEM Research Unit, Eindhoven University of Technology, PO Box 513, Eindhoven, 5600, MB, The Netherlands

    Nico A. J. M. Sommerdijk

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  1. Thomas M. Hermans
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Contributions

T.M.H. wrote the paper and performed NMR and viscosity measurements and performed the analysis of the fractal dimension of the WBP reconstruction from cryo-electron tomography. M.A.C.B. contributed materials. N.G. and G.F. performed and analysed light-scattering experiments. N.A.J.M.S. performed cryo-electron microscopy and tomography and analysis. P.V.D.S. helped with the theoretical understanding of the coupled equilibria. All authors discussed the results and commented on the manuscript.

Corresponding author

Correspondence to E. W. Meijer.

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Hermans, T., Broeren, M., Gomopoulos, N. et al. Self-assembly of soft nanoparticles with tunable patchiness. Nature Nanotech 4, 721–726 (2009). https://doi.org/10.1038/nnano.2009.232

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