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Charged nanoparticles as supramolecular surfactants for controlling the growth and stability of microcrystals

Nature Materials volume 11, pages 227–232 (2012)Cite this article

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Abstract

Microcrystals of desired sizes are important in a range of processes and materials, including controlled drug release1,2, production of pharmaceutics and food3,4, bio-5 and photocatalysis6, thin-film solar cells7 and antibacterial fabrics8. The growth of microcrystals can be controlled by a variety of agents, such as multivalent ions9, charged small molecules10, mixed cationic–anionic surfactants11,12, polyelectrolytes13,14 and other polymers15, micropatterned self-assembled monolayers16,17, proteins18 and also biological organisms during biomineralization19,20. However, the chief limitation of current approaches is that the growth-modifying agents are typically specific to the crystalizing material. Here, we show that oppositely charged nanoparticles can function as universal surfactants that control the growth and stability of microcrystals of monovalent or multivalent inorganic salts, and of charged organic molecules. We also show that the solubility of the microcrystals can be further tuned by varying the thickness of the nanoparticle surfactant layers and by reinforcing these layers with dithiol crosslinks.

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Figure 1: NP surfactants control the growth of inorganic salt microcrystals.
Figure 2: The nature of the assembling structures depends on the ratio of NP and salt concentrations, χ=CNP/Csalt.
Figure 3: Time course of crystallization and crystal-size control.
Figure 4: Varying the thickness of the NP shell and controlling the microcrystals’ solubility.

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Change history

  • 20 January 2012

    In the version of this Letter originally published online, the name of the penultimate author was spelt incorrectly; it should have read Shuangbing Han. This error has been corrected in all versions of the Letter.

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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 under award number DE-SC0000989.

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Authors and Affiliations

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

    Bartlomiej Kowalczyk, Istvan Lagzi, Dawei Wang, Yanhu Wei, Shuangbing Han & Bartosz A. Grzybowski

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

    Bartlomiej Kowalczyk, Istvan Lagzi, Yanhu Wei, Shuangbing Han & Bartosz A. Grzybowski

  3. Department of Chemical Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802, USA

    Kyle J. M. Bishop

Authors
  1. Bartlomiej Kowalczyk
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  2. Kyle J. M. Bishop
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  4. Dawei Wang
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  5. Yanhu Wei
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  7. Bartosz A. Grzybowski
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Contributions

B.K. carried out the majority of experiments and imaging studies, and produced the figures; K.J.M.B. developed theoretical models; I.L. and D.W. helped with NP synthesis; Y.W. and S.H. collected and interpreted crystallographic data; B.A.G. conceived the project and wrote the paper.

Corresponding author

Correspondence to Bartosz A. Grzybowski.

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The authors declare no competing financial interests.

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Kowalczyk, B., Bishop, K., Lagzi, I. et al. Charged nanoparticles as supramolecular surfactants for controlling the growth and stability of microcrystals. Nature Mater 11, 227–232 (2012). https://doi.org/10.1038/nmat3202

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