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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Kalsin, A. M. et al. Electrostatic self-assembly of binary nanoparticle crystals with a diamond-like lattice. Science 312, 420–424 (2006).
Shevchenko, E. V., Talapin, D. V., Kotov, N. A., O'Brien, S. & Murray, C. B. Structural diversity in binary nanoparticle superlattices. Nature 439, 55–59 (2006).
Herlihy, K. P., Nunes, J. & DeSimone, J. M. Electrically driven alignment and crystallization of unique anisotropic polymer particles. Langmuir 24, 8421–8426 (2008).
Han, L. et al. Novel interparticle spatial properties of hydrogen-bonding mediated nanoparticle assembly. Chem. Mater. 15, 29–37 (2003).
Ni, W., Mosquera, R. A., Perez-Juste, J. & Liz-Marzan, L. M. Evidence for hydrogen-bonding-directed assembly of gold nanorods in aqueous solution. J. Phys. Chem. Lett. 1, 1181–1185 (2010).
Mirkin, C. A., Letsinger, R. L., Mucic, R. C. & Storhoff, J. J. A DNA-based method for rationally assembling nanoparticles into macroscopic materials. Nature 382, 607–609 (1996).
Park, S. Y. et al. DNA-programmable nanoparticle crystallization. Nature 451, 553–556 (2008).
Caswell, K. K., Wilson, J. N., Bunz, U. H. F. & Murphy, C. J. Preferential end-to-end assembly of gold nanorods by biotin–streptavidin connectors. J. Am. Chem. Soc. 125, 13914–13915 (2003).
Salem, A. K., Chen, M., Hayden, J., Leong, K. W. & Searson, P. C. Directed assembly of multisegment Au/Pt/Au nanowires. Nano Lett. 4, 1163–1165 (2004).
Alivisatos, A. P. et al. Organization of ‘nanocrystal molecules’ using DNA. Nature 382, 609–611 (1996).
Nykypanchuk, D., Maye, M. M., van der Lelie, D. & Gang, O. DNA-guided crystallization of colloidal nanoparticles. Nature 451, 549–552 (2008).
Chen, C-L., Zhang, P. & Rosi, N. L. A new peptide-based method for the design and synthesis of nanoparticle superstructures: construction of highly ordered gold nanoparticle double helices. J. Am. Chem. Soc. 130, 13555–13557 (2008).
Jones, M. R. et al. DNA–nanoparticle superlattices formed from anisotropic building blocks. Nature Mater. 9, 913–917 (2010).
Macfarlane, R. J. et al. Assembly and organization processes in DNA-directed colloidal crystallization. Proc. Natl Acad. Sci. USA 106, 10493–10498 (2009).
Macfarlane, R. J. et al. Establishing the design rules for DNA-mediated programmable colloidal crystallization. Angew. Chem. Int. Ed. 49, 4589–4592 (2010).
Macfarlane, R. J. et al. Nanoparticle superlattice engineering with DNA. Science 334, 204–208 (2011).
Tan, S. J., Campolongo, M. J., Luo, D. & Cheng, W. L. Building plasmonic nanostructures with DNA. Nature Nanotech. 6, 268–276 (2011).
Cutler, J. I. et al. Polyvalent nucleic acid nanostructures. J. Am. Chem. Soc. 133, 9254–9257 (2011).
Hill, H. D. et al. Controlling the lattice parameters of gold nanoparticle FCC crystals with duplex DNA linkers. Nano Lett. 8, 2341–2344 (2008).
Rupich, S. M., Shevchenko, E. V., Bodnarchuk, M. I., Lee, B. & Talapin, D. V. Size-dependent multiple twinning in nanocrystal superlattices. J. Am. Chem. Soc. 132, 289–296 (2010).
Ye, X., Chen, J. & Murray, C. B. Polymorphism in self-assembled AB6 binary nanocrystal superlattices. J. Am. Chem. Soc. 133, 2613–2620 (2011).
Bodnarchuk, M. I., Kovalenko, M. V., Heiss, W. & Talapin, D. V. Energetic and entropic contributions to self-assembly of binary nanocrystal superlattices: temperature as the structure-directing factor. J. Am. Chem. Soc. 132, 11967–11977 (2010).
Redl, F. X., Cho, K-S., Murray, C. B. & O'Brien, S. Three-dimensional binary superlattices of magnetic nanocrystals and semiconductor quantum dots. Nature 423, 968–971 (2003).
Zhuang, J. et al. Cylindrical superparticles from semiconductor nanorods. J. Am. Chem. Soc. 131, 6084–6085 (2009).
Hu, Y., Uzun, O., Dubois, C. & Stellacci, F. Effect of ligand shell structure on the interaction between monolayer-protected gold nanoparticles. J. Phys. Chem. C 112, 6279–6284 (2008).
Xiong, H., Lelie, D.v.d. & Gang, O. Phase behavior of nanoparticles assembled by DNA linkers. Phys. Rev. Lett. 102, 015504 (2009).
Talapin, D. V., Shevchenko, E. V., Murray, C. B., Titov, A. V. & Kral, P. Dipole–dipole interactions in nanoparticle superlattices. Nano Lett. 7, 1213–1219 (2007).
Sun, D. & Gang, O. Binary heterogeneous superlattices assembles from quantum dots and gold nanoparticles with DNA. J. Am. Chem. Soc. 133, 5252–5254 (2011).
Zhang, K. et al. Nanopod formation through gold nanoparticle templated and catalyzed cross-linking of polymers bearing pendant propargyl ethers. J. Am. Chem. Soc. 132, 15151–15153 (2010).
Jin, R., Wu, G., Li, Z., Mirkin, C. A. & Schatz, G. C. What controls the melting properties of DNA-linked gold nanoparticle assemblies? J. Am. Chem. Soc. 125, 1643–1654 (2003).
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.
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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