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Publication Title | Assembly of reconfigurable one-dimensional colloidal superlattices due to a synergy of fundamental nanoscale forces

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In this work, we have shown that depletion forces acting in synergy with electrostatic forces are a powerful tool for assembling nanoscale anisotropic particles with interparticle spacings on the order of or larger than the dimensions of the nanoparticle building blocks. Using highly anisotropic nanoprisms in a solution of CTAB micelles, we were able to access a regime wherein two fundamental forces are of comparable strength, leading to unique one-dimen- sional superlattice structures which are, themselves, stable colloids. We have shown, both experimentally and theoretically, that the anomalously large d spacings of the lamellar superlattices are the result of an equilibrium between attractive depletion and van der Waals forces and repulsive electrostatic forces. We have also shown that the lattice parameters of the lamellar crystals are reversibly tunable between 17 and 30 nm, almost a factor of two, simply by changing the concentration of the CTAB surfactant, the tem- perature, and/or the ionic strength of the solution. Finally, by in- ducing the lamellar ordering of gold nanoprisms in solution, we have developed a methodology to efficiently separate nanoprisms from spherical nanoparticles formed concomitantly during synth- esis. The stimuli-responsive behavior of the nanoprism superlat- tices suggests that this method of assembling nanoscale colloids

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ACKNOWLEDGMENTS. K.L.Y. acknowledges Dr. Ken Littrell at Oak Ridge National Laboratory for assistance with SANS studies. C.A.M and G.C.S. acknowledge the Department of Energy Office (DOE Award DE-SC0000989) for support through the Northwestern University Nonequilibrium Energy Research Center. C.A.M. is also grateful for a National Security Science and Engineering Faculty Fellowship from the Department of Defense. K.L.Y. acknowledges the National Science Foundation and the National Defense Science and Engineering Graduate Re- search Fellowships. M.R.J. and R.J.M. acknowledge Northwestern University for Ryan Fellowships. R.E.-S. acknowledges Dirección General Asuntos del Per- sonal Académico-Universidad Nacional Autónoma de México, Consejo Nacional de Ciencia y Tecnologia Project 82474. Use of the Advanced Photon Source was supported by the Office of Basic Energy Sciences, US DOE under Contract DE- AC02-06CH11357. The transmission electron microscopy work was carried out in the Electron Probe Instrumentation Center facility of Northwestern University Atomic and Nanoscale Characterization Experimental Center.

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PNAS ∣ February 14, 2012 ∣ vol. 109 ∣ no. 7 ∣ 2245


Image | Assembly of reconfigurable one-dimensional colloidal superlattices due to a synergy of fundamental nanoscale forces

depletion forces synergy electrostatic powerful assembl nanoscale anisotropic particles interparticle
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