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Synthetically programmable nanoparticle superlattices using a hollow three-dimensional spacer approach

Abstract

Crystalline nanoparticle arrays and superlattices with well-defined geometries can be synthesized by using appropriate electrostatic1,2,3, hydrogen-bonding4,5 or biological recognition interactions6,7,8,9,10,11. Although superlattices with many distinct geometries can be produced using these approaches, the library of achievable lattices could be increased by developing a strategy that allows some of the nanoparticles within a binary lattice to be replaced with ‘spacer’ entities that are constructed to mimic the behaviour of the nanoparticles they replace, even though they do not contain an inorganic core. The inclusion of these spacer entities within a known binary superlattice would effectively delete one set of nanoparticles without affecting the positions of the other set. Here, we show how hollow DNA nanostructures can be used as ‘three-dimensional spacers’ within nanoparticle superlattices assembled through programmable DNA interactions7,11,12,13,14,15,16. We show that this strategy can be used to form superlattices with five distinct symmetries, including one that has never before been observed in any crystalline material.

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Figure 1: Use of a three-dimensional spacer in DNA-programmable crystallization of gold nanoparticles.
Figure 2: SAXS data for seven distinct gold nanoparticle superlattices and ‘lattice X’.
Figure 3: SAXS data for cubic lattices made from nanoparticles of different sizes.
Figure 4: TEM images of the AB6-type lattices.

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Acknowledgements

C.A.M. acknowledges support for the Northwestern Nonequilibrium Energy Research Center from the DOE (DE-SC0000989) as well as support from the AFOSR and the DoD (for an NSSEF Fellowship). E.A. acknowledges a Graduate Research Fellowship from the NDSEG. E.A., R.J.M., M.R.J. and K.D.O. acknowledge Ryan Fellowships from Northwestern University. M.R.J. and K.D.O. acknowledge Graduate Research Fellowships from the NSF. SAXS experiments were carried out at the Dupont–Northwestern–Dow Collaborative Access Team beam line at the Advanced Photon Source (APS), Argonne National Laboratory, and use of the APS was supported by the DOE (DE-AC02-06CH11357). The TEM work was performed in the EPIC facility of the NUANCE Center at Northwestern University.

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Contributions

E.A. and J.I.C. designed the experiments, prepared the materials, collected and analysed the data, and wrote the manuscript. R.J.M. designed the experiments and collected and analysed the data. M.R.J. collected and analysed the data. J.W. and G.L. analysed data for the tomography experiments. K.Z. and K.D.O. designed the experiments. C.A.M. designed the experiments and wrote the manuscript.

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Correspondence to Chad A. Mirkin.

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The authors declare no competing financial interests.

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Auyeung, E., Cutler, J., Macfarlane, R. et al. Synthetically programmable nanoparticle superlattices using a hollow three-dimensional spacer approach. Nature Nanotech 7, 24–28 (2012). https://doi.org/10.1038/nnano.2011.222

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