Crystallization is a fundamental and ubiquitous process much studied over the centuries. But although the crystallization of atoms is fairly well understood1,2, it remains challenging to predict reliably the outcome of molecular crystallization processes that are complicated by various molecular interactions and solvent involvement. This difficulty also applies to nanoparticles: high-quality three-dimensional crystals3,4,5,6 are mostly produced using drying and sedimentation techniques that are often impossible to rationalize and control to give a desired crystal symmetry, lattice spacing and habit (crystal shape). In principle, DNA-mediated assembly of nanoparticles offers an ideal opportunity for studying nanoparticle crystallization7,8,9,10,11,12,13,14,15,16,17: a well-defined set of rules have been developed to target desired lattice symmetries and lattice constants8,9,18, and the occurrence of features such as grain boundaries and twinning in DNA superlattices and traditional crystals comprised of molecular or atomic building blocks suggests that similar principles govern their crystallization. But the presence of charged biomolecules, interparticle spacings of tens of nanometres, and the realization so far of only polycrystalline DNA-interconnected nanoparticle superlattices, all suggest that DNA-guided crystallization may differ from traditional crystal growth. Here we show that very slow cooling, over several days, of solutions of complementary-DNA-modified nanoparticles through the melting temperature of the system gives the thermodynamic product with a specific and uniform crystal habit. We find that our nanoparticle assemblies have the Wulff equilibrium crystal structure that is predicted from theoretical considerations and molecular dynamics simulations, thus establishing that DNA hybridization can direct nanoparticle assembly along a pathway that mimics atomic crystallization.
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C.A.M. and M.O.d.l.C. acknowledge support from the following awards: the Air Force Office of Scientific Research (AFOSR) Multidisciplinary University Research Initiative (MURI) FA9550-11-1-0275, the National Science Foundation Materials Research Science and Engineering Center programme DMR-1121262 at the Materials Research Center of Northwestern University, and the Non-equilibrium Energy Research Center (NERC), an Energy Frontier Research Center funded by the Department of Energy (DoE), Office of Science, Office of Basic Energy Sciences under Award DE-SC0000989. E.A. acknowledges a National Defense Science and Engineering Graduate (NDSEG) Fellowship (number 32 CFR 168a). T.L. acknowledges a Ryan Fellowship from Northwestern University. T.L. thanks S. Dhakal and K. Kohlstedt for sharing scripts on the colloid model and S. Patala and J. Zwanikken for discussions. SAXS experiments were carried out at the Dupont–Northwestern–Dow Collaborative Access Team beam line at the Advanced Photon Source (APS) at Argonne National Laboratory, and use of the APS was supported by the DoE (DE-AC02-06CH11357). The electron microscopy work was performed at the Electron Probe Instrumentation Center of the NU Atomic and Nanoscale Characterization Experimental Center at Northwestern University. The computational work was performed using the TARDIS computer cluster supported by the US Department of Defense National Security Science and Engineering Faculty Fellowship (number FA9550-10-1-0167).
The authors declare no competing financial interests.
This file contains Supplementary Materials and Methods, a Supplementary Discussion, Supplementary Figures 1-15, Supplementary Tables 1-2 and additional references. (PDF 2574 kb)
MD Simulations of Rhombic Dodecahedra Microcrystal Formation from Coarse-Grained DNA-Nanoparticle Building Blocks
DNA-nanoparticles coarse-grained as a single bead interact with other beads via electrostatic repulsions and complementary sticky end attractions at ~ 0.95 Tmelt. Consistent with experimental observations, a rhombic dodecahedron microcrystal forms gradually over time. (MOV 16744 kb)
MD Simulations of Formation of FCC Superlattice Grains from Coarse-Grained DNA-Nanoparticle Building Blocks
DNA-nanoparticles coarse-grained as a single bead interact with other beads via electrostatic repulsions and complementary sticky end attractions. Consistent with experimental observations, single crystal Wulff shapes are not observed. (MOV 19016 kb)
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Auyeung, E., Li, T., Senesi, A. et al. DNA-mediated nanoparticle crystallization into Wulff polyhedra. Nature 505, 73–77 (2014). https://doi.org/10.1038/nature12739
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