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Geometric curvature controls the chemical patchiness and self-assembly of nanoparticles

Nature Nanotechnology volume 8, pages 676–681 (2013)Cite this article

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Abstract

When organic molecules are tethered onto non-spherical nanoparticles, their chemical properties depend on the particles’ local curvature and shape. Based on this observation, we show here that it is possible to engineer chemical patchiness across the surface of a non-spherical nanoparticle using a single chemical species. In particular, when acidic ligands are used, regions of the particle surface with different curvature become charged at different pH values of the surrounding solution. This interplay between particle shape and local electrostatics allows for fine control over nanoscale self-assembly leading to structures with varying degrees of complexity. These structures range from particle cross-stacks to open-lattice crystals, the latter with pore sizes on the order of tens of nanometres, that is, at the lower synthetic limits of metallic mesoporous materials.

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Figure 1: Nano-objects with varying curvatures.
Figure 2: Titration of negatively charged particles.
Figure 3: Quantification of the properties of ‘patchy’ anisotropic nano-objects.
Figure 4: Assemblies arising from electrostatic patchiness.
Figure 5: Three-dimensional, porous crystals assembled from charge-patchy nano-dumbbells.

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Acknowledgements

This work was supported by the Non-equilibrium Energy Research Center, which is an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences (award no. DE-SC0000989). D.A.W. acknowledges support provided by the National Science Foundation (NSF) MRSEC program (DMR-1121262) at Northwestern University and the Ryan Fellowship programme.

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Authors and Affiliations

  1. Department of Chemical and Biological Engineering, Northwestern University, 2145 Sheridan Road, Evanston, 60208, Illinois, USA

    David A. Walker, Emily K. Leitsch & Bartosz A. Grzybowski

  2. Department of Biomedical Engineering, Northwestern University, 2145 Sheridan Road, Evanston, 60208, Illinois, USA

    Rikkert J. Nap & Igal Szleifer

  3. Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, 60208, Illinois, USA

    Igal Szleifer & Bartosz A. Grzybowski

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  1. David A. Walker
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Contributions

D.A.W. and E.K.L. performed the experiments and analysis of the experimental results. R.J.N. and I.S. provided theoretical analysis of pKa data. D.A.W. performed theoretical analysis of interacting particles. D.A.W. and B.A.G. conceived the experiments and wrote the paper.

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Correspondence to Bartosz A. Grzybowski.

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Walker, D., Leitsch, E., Nap, R. et al. Geometric curvature controls the chemical patchiness and self-assembly of nanoparticles. Nature Nanotech 8, 676–681 (2013). https://doi.org/10.1038/nnano.2013.158

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