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Re-entrant melting as a design principle for DNA-coated colloids

Nature Materials volume 11, pages 518–522 (2012)Cite this article

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Abstract

Colloids functionalized with DNA hold great promise as building blocks for complex self-assembling structures. However, the practical use of DNA-coated colloids (DNACCs) has been limited by the narrowness of the temperature window where the target structures are both thermodynamically stable and kinetically accessible1,2,3,4,5. Here we propose a strategy to design DNACCs, whereby the colloidal suspensions crystallize on cooling and then melt on further cooling. In a phase diagram with such a re-entrant melting, kinetic trapping of the system in non-target structures should be strongly suppressed. We present model calculations and simulations that show that real DNA sequences exist that should bestow this unusual phase behaviour on suitably functionalized colloidal suspensions. We present our results for binary systems, but the concepts that we develop apply to multicomponent systems and should therefore open the way towards the design of truly complex self-assembling colloidal structures.

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Figure 1: Schematic summary of our model and its temperature behaviour.
Figure 2: Comparison of self-consistent mean-field theory and MC simulations.
Figure 3: Effect of changing the relative hybridization free energy between weak and strong bonds δweak−strong on the inter-plate potential versus temperature.
Figure 4: Phase diagram calculated for an equimolar mixture of X and X′colloids.
Figure 5: Degree of crystallinity as a function of density and temperature.

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Acknowledgements

We thank P. Varilly, F. Martinez-Veracoechea and L. Fillion for useful discussions and a critical reading of the manuscript. This work was supported by the European Research Council (ERC) Advanced Grant 227758, the Wolfson Merit Award 2007/R3 of the Royal Society of London and the Engineering and Physical Sciences Research Council (EPSRC) Programme Grant EP/I001352/1.

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Authors and Affiliations

  1. Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, UK

    Stefano Angioletti-Uberti, Bortolo M. Mognetti & Daan Frenkel

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  1. Stefano Angioletti-Uberti
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  3. Daan Frenkel
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Contributions

S.A-U. conceived the model, developed the analytical theory, performed the simulations and analysed the data. B.M.M. developed the analytical theory and analysed the data. D.F. initiated and supervised the research and analysed the data. All three authors contributed to writing the manuscript.

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Correspondence to Stefano Angioletti-Uberti.

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The authors declare no competing financial interests.

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Angioletti-Uberti, S., Mognetti, B. & Frenkel, D. Re-entrant melting as a design principle for DNA-coated colloids. Nature Mater 11, 518–522 (2012). https://doi.org/10.1038/nmat3314

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