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Spontaneous assembly of subnanometre-ordered domains in the ligand shell of monolayer-protected nanoparticles


The properties of materials can be created and improved either by confining their dimensions in the nanoscale or by controlling their nanostructure. We have combined these two concepts, and here we describe a new class of nanostructured nanosized materials that show ordered phase-separated domains at an unprecedented molecular length scale. Scanning tunnelling and transmission electron microscope images of monolayer-protected metal nanoparticles, with ligand shells composed of a mixture of molecules, show that the ligands phase-separate into ordered domains as small as 5 Å. Importantly, the domain shape and dimensions can be controlled by varying the ligand composition or the metallic core size. We demonstrate that the formation of ordered domains depends on the curvature of the underlying substrate, and that novel properties result from this nanostructuring. For example, because the size of the domains is much smaller than the typical dimensions of a protein, these materials are extremely effective in avoiding non-specific adsorption of a variety of proteins.

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Figure 1: MPMNs with phase-separated ordered (rippled) domains on their ligand shell.
Figure 2: Plot of the domain spacing versus the MPA fraction used in the one-step synthesis of gold nanoparticles.
Figure 3: Three-dimensional rendering of STM height images of gold nanoparticles.
Figure 4: The solubility in ethanol of a series of OT/MPA gold nanoparticles as a function of MPA fraction (3.7 nm in diameter).
Figure 5: Schematic drawing of a generic protein (top) and a rippled nanoparticle (bottom).
Figure 6: STM images of mixed OT/MPA monolayers formed on surfaces of varying curvature.


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This work was supported in part by the Material Research Science and Education Center Program of the National Science Foundation under award number DMR 02-13282, and made use of its shared facilities. It was also supported by NIRT DMR-0303973 of the National Science Foundation. J.W.M. acknowledges support by the P. E. Gray fund for undergraduate research. The authors are extremely grateful to Blaise Gassend for his contribution to the synthesis of nanoparticles. Mike Frongillo is acknowledged for his invaluable assistance with the TEM images. Dave Voci, Digital Instruments, is acknowledged for his continuing support.

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Correspondence to Francesco Stellacci.

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Jackson, A., Myerson, J. & Stellacci, F. Spontaneous assembly of subnanometre-ordered domains in the ligand shell of monolayer-protected nanoparticles. Nature Mater 3, 330–336 (2004).

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