DNA-guided crystallization of colloidal nanoparticles

Abstract

Many nanometre-sized building blocks will readily assemble into macroscopic structures. If the process is accompanied by effective control over the interactions between the blocks and all entropic effects1,2, then the resultant structures will be ordered with a precision hard to achieve with other fabrication methods. But it remains challenging to use self-assembly to design systems comprised of different types of building blocks—to realize novel magnetic, plasmonic and photonic metamaterials3,4,5, for example. A conceptually simple idea for overcoming this problem is the use of ‘encodable’ interactions between building blocks; this can in principle be straightforwardly implemented using biomolecules6,7,8,9,10. Strategies that use DNA programmability to control the placement of nanoparticles in one and two dimensions have indeed been demonstrated11,12,13. However, our theoretical understanding of how to extend this approach to three dimensions is limited14,15, and most experiments have yielded amorphous aggregates16,17,18,19 and only occasionally crystallites of close-packed micrometre-sized particles9,10. Here, we report the formation of three-dimensional crystalline assemblies of gold nanoparticles mediated by interactions between complementary DNA molecules attached to the nanoparticles’ surface. We find that the nanoparticle crystals form reversibly during heating and cooling cycles. Moreover, the body-centred-cubic lattice structure is temperature-tuneable and structurally open, with particles occupying only 4% of the unit cell volume. We expect that our DNA-mediated crystallization approach, and the insight into DNA design requirements it has provided, will facilitate both the creation of new classes of ordered multicomponent metamaterials and the exploration of the phase behaviour of hybrid systems with addressable interactions.

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Figure 1: Schematic of experimental design.
Figure 2: Crystallization pathway for system IV.
Figure 3: Structure of crystalline DNA–nanoparticle systems.

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Acknowledgements

We acknowledge the support of the Division Materials Science and Engineering in the Office of Basic Energy Sciences within the US DOE Office of Science. We thank the Center for Functional Nanomaterials and National Synchrotron Light Source at Brookhaven National Laboratory for the use of their facilities.

Author Contributions D.N., M.M.M., D.v.d.L. and O.G. contributed to the design of the experiment. M.M.M. synthesized and functionalized nanoparticles. D.N., M.M.M. and O.G. collected data and prepared the manuscript. D.N. processed X-ray data. O.G. directed the research.

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Correspondence to Oleg Gang.

Supplementary information

Supplementary Information

The file contains Supplementary Discussion on the thermal behavior un-crystallized DNA – nanoparticle systems. It includes Supplementary Figures S1 and S2; Supplementary Tables S1-S3 and additional references pertaining to the Supplementary Discussion. (PDF 717 kb)

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Nykypanchuk, D., Maye, M., van der Lelie, D. et al. DNA-guided crystallization of colloidal nanoparticles. Nature 451, 549–552 (2008). https://doi.org/10.1038/nature06560

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