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Probing interfacial equilibration in microsphere crystals formed by DNA-directed assembly

Abstract

DNA is the premier material for directing nanoscale self-assembly, having been used to produce many complex forms1,2,3,4. Recently, DNA has been used to direct colloids5,6 and nanoparticles7,8 into novel crystalline structures, providing a potential route to fabricating meta-materials9 with unique optical properties. Although theory10,11,12 has sought the crystal phases that minimize total free energy, kinetic barriers13 remain essentially unstudied. Here we study interfacial equilibration in a DNA-directed microsphere self-assembly system5,6,14 and carry out corresponding detailed simulations. We introduce a single-nucleotide difference in the DNA strands on two mixed microsphere species, which generates a free-energy penalty5,15,16 for inserting ‘impurity’ spheres into a ‘host’ sphere crystal, resulting in a reproducible segregation coefficient. Comparison with simulation reveals that, under our experimental conditions, particles can equilibrate only with a few nearest neighbours before burial by the growth front, posing a potential impediment to the growth of complex structures.

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Figure 1: Polymer microspheres grafted with single-stranded DNA can form solid-solution colloidal crystals.
Figure 2: Varying the DNA sequence alters the experimental segregation coefficients of binary colloidal crystals.
Figure 3: Simulation results show that segregation is controlled by the crystal growth rate.
Figure 4: Different segregation steps correspond to the rates of particle escape from different configurations.

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Acknowledgements

These studies were supported by the National Science Foundation under the DMR, NIRT and MRSEC programs. We thank A. Alsayed, Y. Han, V.N. Manoharan, V. T. Milam, M. Ung and M.-P. Valignat for discussions.

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The experiments were designed by A.J.K., P.L.B. and J.C.C., implemented by A.J.K., and analysed by A.J.K., T.S. and J.C.C. The simulations were designed by R.S. and T.S., implemented by R.S. and interpreted by R.S., J.C.C. and T.S. The interaction model was implemented by R.S. and P.L.B. J.C.C. and T.S. wrote the manuscript and oversaw the project.

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Correspondence to John C. Crocker.

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Kim, A., Scarlett, R., Biancaniello, P. et al. Probing interfacial equilibration in microsphere crystals formed by DNA-directed assembly. Nature Mater 8, 52–55 (2009). https://doi.org/10.1038/nmat2338

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