It was first shown1,2 more than ten years ago that DNA oligonucleotides can be attached to gold nanoparticles rationally to direct the formation of larger assemblies. Since then, oligonucleotide-functionalized nanoparticles have been developed into powerful diagnostic tools3,4 for nucleic acids and proteins, and into intracellular probes5 and gene regulators6. In contrast, the conceptually simple yet powerful idea that functionalized nanoparticles might serve as basic building blocks that can be rationally assembled through programmable base-pairing interactions into highly ordered macroscopic materials remains poorly developed. So far, the approach has mainly resulted in polymerization, with modest control over the placement of, the periodicity in, and the distance between particles within the assembled material. That is, most of the materials obtained thus far are best classified as amorphous polymers7,8,9,10,11,12,13,14,15,16, although a few examples of colloidal crystal formation exist8,16. Here, we demonstrate that DNA can be used to control the crystallization of nanoparticle–oligonucleotide conjugates to the extent that different DNA sequences guide the assembly of the same type of inorganic nanoparticle into different crystalline states. We show that the choice of DNA sequences attached to the nanoparticle building blocks, the DNA linking molecules and the absence or presence of a non-bonding single-base flexor can be adjusted so that gold nanoparticles assemble into micrometre-sized face-centred-cubic or body-centred-cubic crystal structures. Our findings thus clearly demonstrate that synthetically programmable colloidal crystallization is possible, and that a single-component system can be directed to form different structures.
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C.A.M. acknowledges the AFOSR and NSF for support of this work. C.A.M is also grateful for a NIH Director’s Pioneer Award. S.Y.P. and G.C.S. were supported by the NSF. S.Y.P. and G.C.S. thank S. Torquato for providing numerical model output and S. Ryu for discussions. We thank S. Seifert for help with the SAXS set-up. We thank the Argonne National Laboratory for the use of the APS, supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences.
Author Contributions C.A.M. was the originator of the concept of programmable colloidal crystallization with DNA. A.K.R.L.-J. and C.A.M were responsible for the synthetic components of the project and sequence design. S.Y.P. and G.C.S. were responsible for the theoretical components of the project. S.W. designed the SAXS set-up. S.Y.P., A.K.R.L.-J. and B.L. designed and performed SAXS experiments. S.Y.P. and B.L. analysed the SAXS data. All authors contributed to the writing of the manuscript.
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Park, S., Lytton-Jean, A., Lee, B. et al. DNA-programmable nanoparticle crystallization. Nature 451, 553–556 (2008). https://doi.org/10.1038/nature06508
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