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Surface patterning of nanoparticles with polymer patches

Nature volume 538, pages 79–83 (2016)Cite this article

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Abstract

Patterning of colloidal particles with chemically or topographically distinct surface domains (patches) has attracted intense research interest1,2,3. Surface-patterned particles act as colloidal analogues of atoms and molecules4,5, serve as model systems in studies of phase transitions in liquid systems6, behave as ‘colloidal surfactants’7 and function as templates for the synthesis of hybrid particles8. The generation of micrometre- and submicrometre-sized patchy colloids is now efficient9,10,11, but surface patterning of inorganic colloidal nanoparticles with dimensions of the order of tens of nanometres is uncommon. Such nanoparticles exhibit size- and shape-dependent optical, electronic and magnetic properties, and their assemblies show new collective properties12. At present, nanoparticle patterning is limited to the generation of two-patch nanoparticles13,14,15, and nanoparticles with surface ripples16 or a ‘raspberry’ surface morphology17. Here we demonstrate nanoparticle surface patterning, which utilizes thermodynamically driven segregation of polymer ligands from a uniform polymer brush into surface-pinned micelles following a change in solvent quality. Patch formation is reversible but can be permanently preserved using a photocrosslinking step. The methodology offers the ability to control the dimensions of patches, their spatial distribution and the number of patches per nanoparticle, in agreement with a theoretical model. The versatility of the strategy is demonstrated by patterning nanoparticles with different dimensions, shapes and compositions, tethered with various types of polymers and subjected to different external stimuli. These patchy nanocolloids have potential applications in fundamental research, the self-assembly of nanomaterials, diagnostics, sensing and colloidal stabilization.

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Figure 1: Polymer segregation on the nanoparticle surface.
Figure 2: Structural transitions in the polymer layer on the surface of gold nanospheres.
Figure 3: Generality of polymer patterning of nanoparticle surface.
Figure 4: Self-assembly of patterned nanoparticles.

Change history

  • 05 October 2016

    Present addresses were added for author O.G., who is currently associated with the Center for Functional Nanomaterials, Brookhaven National Laboratory, and with the Departments of Chemical Engineering and of Applied Physics and Applied Mathematics at Columbia University.

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Acknowledgements

We thank the Connaught Foundation and the National Science and Engineering Research Council of Canada (Discovery and Canada Research Chair programmes) for financial support of this work. E.B.Z. acknowledges partial support from the Russian Foundation for Basic Research (grant 14-03-00372a) and from the Government of Russian Federation (grant 074-U01). M.R. acknowledges financial support from the National Science Foundation (grants DMR-1309892, DMR-1436201 and DMR-1121107), the National Institutes of Health (grants P01-HL108808 and 1UH2HL123645), and the Cystic Fibrosis Foundation. Research was in part carried out at the Center for Functional Nanomaterials, Brookhaven National Laboratory supported by the US Department of Energy, Office of Basic Energy Sciences (under contract number DE-SC0012704). R.M.C. acknowledges the Natural Sciences and Engineering Research Council of Canada for a PGS-D scholarship. A.K. acknowledges an Ontario Trillium Scholarship. We thank M. Michaelis and S. Lin for initiating preliminary experiments and I. Gourevich for help with imaging experiments.

Author information

Author notes

  1. Oleg Gang

    Present address: †Present addresses: Department of Chemical Engineering, Columbia University, New York 10027, USA; Department of Applied Physics and Applied Mathematics, Columbia University, New York 10027, USA.,

Authors and Affiliations

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

    Rachelle M. Choueiri, Elizabeth Galati, Héloïse Thérien-Aubin, Anna Klinkova, Egor M. Larin, Ana Querejeta-Fernández & Eugenia Kumacheva

  2. Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, 11973, New York, USA

    Lili Han, Huolin L. Xin & Oleg Gang

  3. Institute of New Energy Materials, School of Materials Science and Engineering, Tianjin University,, Tianjin, 300072, China

    Lili Han

  4. Institute of Macromolecular Compounds of the Russian Academy of Sciences, Saint Petersburg, 199004, Russia

    Ekaterina B. Zhulina

  5. Saint Petersburg National University of Informational Technologies, Mechanics and Optics, 197101, Saint Petersburg, Russia

    Ekaterina B. Zhulina

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

    Michael Rubinstein

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

    Eugenia Kumacheva

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

    Eugenia Kumacheva

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Contributions

E.K. and R.M.C. proposed the approach and designed the experiments for nanoparticle surface patterning. R.M.C. synthesized and surface-patterned polystyrene-coated gold nanospheres, nanodumbbells and nanorods, and conducted self-assembly experiments of patchy nanospheres in the presence of excess polymer. E.G. synthesized and surface-patterned polystyrene-capped gold nanospheres and silver nanocubes, as well as poly(N-vinyl carbazole)-functionalized nanospheres. E.G. and E.M.L. determined polystyrene grafting density on nanosphere surfaces. H.T.-A. synthesized polystyrene-co-PI and poly(4-vinyl pyridine) and surface-patterned nanosphere surfaces. R.M.C., E.G. and H.T.-A. statistically characterized the morphology of patchy nanospheres. A.K. synthesized triangular silver nanoprisms and nanocubes and conducted experiments on nanocube self-assembly. A.Q.-F. surface-patterned gold nanocubes and conducted self-assembly of patchy nanospheres. L.H. performed tomography experiments and H.L.X. and O.G. interpreted the data. E.B.Z. and M.R. developed the theoretical model describing polymer segregation on the nanosphere surface.

Corresponding author

Correspondence to Eugenia Kumacheva.

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The authors declare no competing financial interests.

Additional information

Reviewer Information

Nature thanks I. Kretzschmar, D. Williams and the other anonymous reviewer(s) for their contribution to the peer review of this work.

Supplementary information

Supplementary Information

This file contains a description of the methods (synthesis, surface functionalization, polymer segregation experiments, self-assembly experiments, tomography, cross-linking), a description of the theoretical model with relevant equations, Supplementary Figures 1-27 (characterization of nanoparticles, statistical analyses of patchy species, schematics for theoretical model) and Supplementary Tables 1-3 (summaries of conditions used in methods). (PDF 4203 kb)

A rotational view of three dimensional reconstruction of the polymer coated gold particle around the x-axis

A rotational view of three dimensional reconstruction of the polymer coated gold particle around the x-axis (MPG 18417 kb)

A rotational view of three dimensional reconstruction of the polymer coated gold particle around the y-axis

A rotational view of three dimensional reconstruction of the polymer coated gold particle around the y-axis (MPG 18113 kb)

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Choueiri, R., Galati, E., Thérien-Aubin, H. et al. Surface patterning of nanoparticles with polymer patches. Nature 538, 79–83 (2016). https://doi.org/10.1038/nature19089

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