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

Abstract

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.

References

  1. Templeton, A.C., Wuelfing, M.P. & Murray, R.W. Monolayer protected cluster molecules. Acc. Chem. Res. 33, 27–36 (2000).

    CAS  Article  Google Scholar 

  2. Alivisatos, A.P. Semiconductor clusters, nanocrystals, and quantum dots. Science 271, 933–937 (1996).

    CAS  Article  Google Scholar 

  3. Daniel, M.C. & Astruc, D. Gold nanoparticles: Assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology. Chem. Rev. 104, 293–346 (2004).

    CAS  Article  Google Scholar 

  4. Thomas, K.G. & Kamat, P.V. Chromophore-functionalized gold nanoparticles. Acc. Chem. Res. 36, 888–898 (2003).

    CAS  Article  Google Scholar 

  5. Xia, Y.N. et al. One-dimensional nanostructures: Synthesis, characterization, and applications. Adv. Mater. 15, 353–389 (2003).

    CAS  Article  Google Scholar 

  6. Hu, J.T., Odom, T.W. & Lieber, C.M. Chemistry and physics in one dimension: Synthesis and properties of nanowires and nanotubes. Acc. Chem. Res. 32, 435–445 (1999).

    CAS  Article  Google Scholar 

  7. Dai, H.J. Carbon nanotubes: Synthesis, integration, and properties. Acc. Chem. Res. 35, 1035–1044 (2002).

    CAS  Article  Google Scholar 

  8. Empedocles, S.A., Neuhauser, R., Shimizu, K. & Bawendi, M.G. Photoluminescence from single semiconductor nanostructures. Adv. Mater. 11, 1243–1256 (1999).

    CAS  Article  Google Scholar 

  9. Schiotz, J., Di Tolla, F.D. & Jacobsen, K.W. Softening of nanocrystalline metals at very small grain sizes. Nature 391, 561–563 (1998).

    Article  Google Scholar 

  10. Bockstaller, M., Kolb, R. & Thomas, E.L. Metallodielectric photonic crystals based on diblock copolymers. Adv. Mater. 13, 1783–1786 (2001).

    CAS  Article  Google Scholar 

  11. Lauhon, L.J., Gudiksen, M.S., Wang, C.L. & Lieber, C.M. Epitaxial core-shell and core-multishell nanowire heterostructures. Nature 420, 57–61 (2002).

    CAS  Article  Google Scholar 

  12. Oldenburg, S.J., Hale, G.D., Jackson, J.B. & Halas, N.J. Light scattering from dipole and quadrupole nanoshell antennas. Appl. Phys. Lett. 75, 1063–1065 (1999).

    CAS  Article  Google Scholar 

  13. Ulman, A. Formation and structure of self-assembled monolayers. Chem. Rev. 96, 1533–1554 (1996).

    CAS  Article  Google Scholar 

  14. Bain, C.D. & Whitesides, G.M. Modeling organic-surfaces with self-assembled monolayers. Angew. Chem. Intl Edn 28, 506–512 (1989).

    Article  Google Scholar 

  15. Yitzchaik, S. & Marks, T.J. Chromophoric self-assembled superlattices. Acc. Chem. Res. 29, 197–202 (1996).

    CAS  Article  Google Scholar 

  16. Stranick, S.J. et al. Nanometer-scale phase separation in mixed composition self-assembled monolayers. Nanotechnology 7, 438–442 (1996).

    CAS  Article  Google Scholar 

  17. Delamarche, E., Michel, B., Biebuyck, H.A. & Gerber, C. Golden interfaces: The surface of self-assembled monolayers. Adv. Mater. 8, 719–724 (1996).

    CAS  Article  Google Scholar 

  18. Folkers, J.P., Laibinis, P.E. & Whitesides, G.M. Self-Assembled monolayers of alkanethiols on gold - comparisons of monolayers containing mixtures of short-chain and long-chain constituents with CH3 and CH2OH terminal groups. Langmuir 8, 1330–1341 (1992).

    CAS  Article  Google Scholar 

  19. Smith, R.K. et al. Phase separation within a binary self-assembled monolayer on Au{111} driven by an amide-containing alkanethiol. J. Phys. Chem. B 105, 1119–1122 (2001).

    CAS  Article  Google Scholar 

  20. Imabayashi, S., Gon, N., Sasaki, T., Hobara, D. & Kakiuchi, T. Effect of nanometer-scale phase separation on wetting of binary self-assembled thiol monolayers on Au(111). Langmuir 14, 2348–2351 (1998).

    CAS  Article  Google Scholar 

  21. Link, S. & El-Sayed, M.A. Spectral properties and relaxation dynamics of surface plasmon electronic oscillations in gold and silver nanodots and nanorods. J. Phys. Chem. B 103, 8410–8426 (1999).

    CAS  Article  Google Scholar 

  22. Andres, R.P. et al. “Coulomb staircase” at room temperature in a self-assembled molecular nanostructure. Science 272, 1323–1325 (1996).

    CAS  Article  Google Scholar 

  23. Brust, M., Walker, M., Bethell, D., Schiffrin, D.J. & Whyman, R. Synthesis of thiol-derivatized gold nanoparticles in a 2-phase liquid-liquid system. J. Chem. Soc. Chem. Commun. 801–802 (1994).

  24. Stellacci, F. et al. Ultrabright supramolecular beacons based on self-assembly of two-photon chromophores on metal nanoparticles. J. Am. Chem. Soc. 125, 328–328 (2003).

    CAS  Article  Google Scholar 

  25. Ingram, R.S., Hostetler, M.J. & Murray, R.W. Poly-hetero-omega-functionalized alkanethiolate-stabilized gold cluster compounds. J. Am. Chem. Soc. 119, 9175–9178 (1997).

    CAS  Article  Google Scholar 

  26. Stellacci, F. et al. Laser and electron-beam induced growth of nanoparticles for 2D and 3D metal patterning. Adv. Mater. 14, 194–198 (2002).

    CAS  Article  Google Scholar 

  27. Sandhyarani, N., Pradeep, T., Chakrabarti, J., Yousuf, M. & Sahu, H.K. Distinct liquid phase in metal-cluster superlattice solids. Phys. Rev. B 62, R739–R742 (2000).

    CAS  Article  Google Scholar 

  28. Fasolka, M.J. & Mayes, A.M. Block copolymer thin films: Physics and applications. Annu. Rev. Mater. Res. 31, 323–355 (2001).

    CAS  Article  Google Scholar 

  29. Hobara, D., Imabayashi, S. & Kakiuchi, T. Preferential adsorption of horse heart cytochrome C on nanometer-scale domains of a phase-separated binary self-assembled monolayer of 3-mercaptopropionic acid and 1-hexadecanethiol on Au(111). Nano Lett. 2, 1021–1025 (2002).

    CAS  Article  Google Scholar 

  30. Satulovsky, J., Carignano, M.A. & Szleifer, I. Kinetic and thermodynamic control of protein adsorption. Proc. Natl Acad. Sci. USA 97, 9037–9041 (2000).

    CAS  Article  Google Scholar 

  31. Kidoaki, S. & Matsuda, T. Adhesion forces of the blood plasma proteins on self-assembled monolayer surfaces of alkanethiolates with different functional groups measured by an atomic force microscope. Langmuir 15, 7639–7646 (1999).

    CAS  Article  Google Scholar 

  32. Nelson, D.R. Toward a tetravalent chemistry of colloids. Nano Lett. 2, 1125–1129 (2002).

    CAS  Article  Google Scholar 

  33. Lu, W. & Suo, Z. Symmetry breaking in self-assembled monolayers on solid surfaces. II. Anisotropic substrate elasticity. Phys. Rev. B 65 (2002).

  34. Song, Y., Huang, T. & Murray, R.W. Heterophase Ligand Exchange and Metal Transfer between Monolayer Protected Clusters. J. Am. Chem. Soc. 125, 11694–11701 (2003).

    CAS  Article  Google Scholar 

  35. Terrill, R.H. et al. Monolayers in three dimensions: NMR, SAXS, thermal, and electron hopping studies of alkanethiol stabilized gold clusters. J. Am. Chem. Soc. 117, 12537–12548 (1995).

    CAS  Article  Google Scholar 

  36. Badia, A. et al. Self-assembled monolayers on gold nanoparticles. Chem. Europ. J. 2, 359–363 (1996).

    CAS  Article  Google Scholar 

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Acknowledgements

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). https://doi.org/10.1038/nmat1116

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