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Perfect mixing of immiscible macromolecules at fluid interfaces

Nature Materials volume 12, pages 735–740 (2013)Cite this article

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Abstract

The difficulty of mixing chemically incompatible substances—in particular macromolecules and colloidal particles—is a canonical problem limiting advances in fields ranging from health care to materials engineering1,2,3,4. Although the self-assembly of chemically different moieties has been demonstrated in coordination complexes, supramolecular structures, and colloidal lattices among other systems5,6,7,8,9,10,11,12,13,14,15,16,17,18, the mechanisms of mixing largely rely on specific interfacing of chemically, physically or geometrically complementary objects. Here, by taking advantage of the steric repulsion between brush-like polymers tethered to surface-active species, we obtained long-range arrays of perfectly mixed macromolecules with a variety of polymer architectures and a wide range of chemistries without the need of encoding specific complementarity. The net repulsion arises from the significant increase in the conformational entropy of the brush-like polymers with increasing distance between adjacent macromolecules at fluid interfaces. This entropic-templating assembly strategy enables long-range patterning of thin films on sub-100 nm length scales.

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Figure 1: Miscibility and entropic templating.
Figure 2: Conventional and novel mixing scenarios at a fluid interface.
Figure 3: Spacing control.
Figure 4: Equilibrium and kinetics.

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Acknowledgements

The authors thank E. T. Samulski for insightful discussions and reviewing the paper. S.S.S., A.V.D., V.V.T. and M.R. acknowledge financial support from the National Science Foundation DMR-0906985, DMR-1004576, DMR-1122483, DMR-1002810 and DMR-0907515.

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Author notes

  1. Dorota Neugebauer

    Present address: Present address: Silesian University of Technology in Gliwice, 44-100 Gliwice, Poland,

Authors and Affiliations

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

    Sergei S. Sheiko, Jing Zhou, Jamie Arnold & Michael Rubinstein

  2. Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, USA

    Dorota Neugebauer & Krzysztof Matyjaszewski

  3. Department of Chemical Engineering, University of Patras, 26504 Patras, Greece

    Constantinos Tsitsilianis

  4. School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332-0245, USA

    Vladimir V. Tsukruk

  5. Institute of Materials Science and Department of Physics, Polymer Program, University of Connecticut, Storrs, Connecticut 06268, USA

    Jan-Michael Y. Carrillo & Andrey V. Dobrynin

Authors
  1. Sergei S. Sheiko
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Contributions

S.S.S. wrote the manuscript and supervised the project, J.Z. and J.A. performed the experiments, D.N. and C.T. synthesized materials, J-M.Y.C. performed Monte Carlo modelling of 2D patterns, A.V.D. and M.R. developed theoretical analysis of interfacial mixing, and K.M. and V.V.T. discussed results and contributed to revisions.

Corresponding author

Correspondence to Sergei S. Sheiko.

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The authors declare no competing financial interests.

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Sheiko, S., Zhou, J., Arnold, J. et al. Perfect mixing of immiscible macromolecules at fluid interfaces. Nature Mater 12, 735–740 (2013). https://doi.org/10.1038/nmat3651

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