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A general approach to DNA-programmable atom equivalents


Nanoparticles can be combined with nucleic acids to programme the formation of three-dimensional colloidal crystals where the particles’ size, shape, composition and position can be independently controlled1,2,3,4,5,6,7. However, the diversity of the types of material that can be used is limited by the lack of a general method for preparing the basic DNA-functionalized building blocks needed to bond nanoparticles of different chemical compositions into lattices in a controllable manner. Here we show that by coating nanoparticles protected with aliphatic ligands with an azide-bearing amphiphilic polymer, followed by the coupling of DNA to the polymer using strain-promoted azide–alkyne cycloaddition8 (also known as copper-free azide–alkyne click chemistry), nanoparticles bearing a high-density shell of nucleic acids can be created regardless of nanoparticle composition. This method provides a route to a virtually endless class of programmable atom equivalents for DNA-based colloidal crystallization.

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Figure 1: Synthesis scheme for nanoparticle-based PAEs.
Figure 2: Characterization of fcc and bcc colloidal superlattices assembled from QD-, DAu- and Fe3O4-PAEs.
Figure 3: Characterization of superlattices assembled from Fe3O4-PAEs of different size.
Figure 4: Binary superlattices assembled from arbitrary combinations of QD-, DAu- and Fe3O4-PAEs.

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C.A.M. acknowledges the support of DoD/NSSEFF/NPS Awards N00244-09-1-0012 and N00244-09-1-0071, AFOSR Awards FA9550-11-1-0275, FA9550-12-1-0280, and FA9550-09-1-0294, the National Science Foundation’s MRSEC programme (DMR-0520513) at the Materials Research Center of Northwestern University, the Defense Advanced Research Projects Agency (DARPA)/Microsystems Technology Office (MTO) under Award Nos HR0011-13-2-0002, HR0011-13-2-0018 and N66001-11-1-4189, and the Non-equilibrium Energy Research Center (NERC), an Energy Frontier Research Center funded by the US DOE, Office of Science, Office of Basic Energy Sciences Award DE-SC0000989 (nanoparticle synthesis). Any opinions, findings, and conclusion or recommendations expressed in this publication are those of the author(s) and do not necessarily reflect the views of the funding agencies, and no official endorsement should be inferred. R.J.M. acknowledges a Ryan Fellowship from Northwestern University. K.L.Y. and E.A. acknowledge National Defense Science and Engineering Graduate Research Fellowships. C.H.J.C. acknowledges a postdoctoral research fellowship from the Croucher Foundation. L.H. acknowledges the HHMI for support from an international student research fellowship. 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 electron microscopy work was performed at the Biological Imaging Facility (BIF) and the Electron Probe Instrumentation Center (EPIC) at Northwestern University.

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C.Z., R.J.M. and C.A.M. initiated the concepts. C.Z. and R.J.M. designed the experiments. C.Z. conducted the experiments. C.Z., R.J.M. and C.A.M. wrote the manuscript. All authors contributed to data collection, data analysis and manuscript preparation.

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Correspondence to Chad A. Mirkin.

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Zhang, C., Macfarlane, R., Young, K. et al. A general approach to DNA-programmable atom equivalents. Nature Mater 12, 741–746 (2013).

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