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Self-assembly of nanoparticles into structured spherical and network aggregates

Nature volume 404, pages 746–748 (2000)Cite this article

Abstract

Multi-scale ordering of materials is central for the application of molecular systems1,2,3 in macroscopic devices4,5. Self-assembly based on selective control of non-covalent interactions6,7,8 provides a powerful tool for the creation of structured systems at a molecular level, and application of this methodology to macromolecular systems provides a means for extending such structures to macroscopic length scale9,10,11. Monolayer-functionalized nanoparticles can be made with a wide variety of metallic and non-metallic cores, providing a versatile building block for such approaches. Here we present a polymer-mediated ‘bricks and mortar’ strategy for the ordering of nanoparticles into structured assemblies. This methodology allows monolayer-protected gold particles to self-assemble into structured aggregates while thermally controlling their size and morphology. Using 2-nm gold particles as building blocks, we show that spherical aggregates of size 97 ± 17 nm can be produced at 23 °C, and that 0.5–1 µm spherical assemblies with (5–40) × 105 individual subunits form at -20 °C. Intriguingly, extended networks of ∼50-nm subunits are formed at 10 °C, illustrating the potential of our approach for the formation of diverse structural motifs such as wires and rods. These findings demonstrate that the assembly process provides control over the resulting aggregates, while the modularity of the ‘bricks and mortar’ approach allows combinatorial control over the constituents, providing a versatile route to new materials systems.

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Figure 1: Recognition motif and polymer ‘mortar’.
Figure 2
Figure 3: Small-angle X-ray scattering of Thy-Au and polymer 1-Thy-Au aggregate.
Figure 4: Proposed mechanism for the aggregation of polymer 1-Thy-Au.
Figure 5: TEM image of polymer 1-Thy-Au aggregates formed at different temperatures.

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References

  1. Anelli,P. L., Spencer,N. & Stoddart, J. F. A molecular shuttle. J. Am. Chem. Soc. 113, 5131–5133 ( 1991).

    Article  CAS  Google Scholar 

  2. Otsuki,J. et al. Redox-responsive molecular switch for intramolecular energy transfer. J. Am. Chem. Soc. 119, 7895– 7896 (1997).

    Article  CAS  Google Scholar 

  3. de Silva,A. P., Gunaratne,H. Q. N. & McCoy, C. P. Molecular photoionic and logic gates with bright fluorescence and “off-on” digital action. J. Am. Chem. Soc. 119, 7891–7892 ( 1997).

    Article  CAS  Google Scholar 

  4. Alivisatos,A. P. From molecules to materials: Current trends and future directions. Adv. Mater. 10, 1297–1336 (1998).

    Article  Google Scholar 

  5. Breen,T. L., Tien,J., Oliver,S. R. J., Hadzic,T. & Whitesides, G. M. Design and self-assembly of open, regular, 3D mesostructures. Science 284, 948–951 (1999).

    Article  ADS  Google Scholar 

  6. Lehn,J.-M. Supramolecular Chemistry (VCH, Weinheim, 1995).

    Book  Google Scholar 

  7. Fyfe,M. C. T. & Stoddart,J. F. Synthetic supramolecular chemistry. Acc. Chem. Res. 30, 393– 401 (1997).

    Article  CAS  Google Scholar 

  8. Rebek,J. Reversible encapsulation and its consequences in solution. Acc. Chem. Res. 32, 278–286 ( 1999).

    Article  CAS  Google Scholar 

  9. Stupp,S. I. et al. Supramolecular materials: Self-organized nanostructures. Science 276, 384–389 ( 1997).

    Article  CAS  Google Scholar 

  10. Kotera,M., Lehn,J. -M. & Vigneron, J. -P. Self-assembled supramolecular rigid rods. J. Chem. Soc. Chem. Commun. 197–199 (1994).

  11. Edgecombe,B. D., Stein,J. A., Fréchet, J. M. J., Xu,Z. & Kramer,E. J. The role of polymer architecture in strengthening polymer-polymer interfaces: A comparison of graft, block, and random copolymers containing hydrogen-bonding moieties. Macromolecules 31, 1292–1304 ( 1998).

    Article  ADS  CAS  Google Scholar 

  12. Andres,R. P. et al. Self-assembly of a two-dimensional superlattice of molecularly linked metal clusters. Science 273, 1690 –1693 (1996).

    Article  ADS  CAS  Google Scholar 

  13. Markovich,G. et al. Architectonic quantum dot solids. Acc. Chem. Res. 32, 415–423 ( 1999).

    Article  CAS  Google Scholar 

  14. Liu,J. et al. Cyclodextrin-modified gold nanospheres. Host-guest interactions at work to control colloidal properties. J. Am. Chem. Soc. 121, 4304–4305 (1999).

    Article  CAS  Google Scholar 

  15. Marinakos,S. M., Brousseau,L. C. III, Jones,A. & Feldheim,D. L. Template synthesis of one-dimensional Au, Au-poly(pyrrole), and poly(pyrrole) nanoparticle arrays. Chem. Mater. 10, 1214 –1219 (1998).

    Article  CAS  Google Scholar 

  16. Whetten,R. L. et al. Crystal structures of molecular gold nanocrystal arrays. Acc. Chem. Res. 32, 397–406 (1999).

    Article  CAS  Google Scholar 

  17. Mucic,R. C., Storhoff,J. J., Mirkin,C. A. & Letsinger,R. L. DNA-directed synthesis of binary nanoparticle network materials. J. Am. Chem. Soc. 120, 12674–12675 (1998).

    Article  CAS  Google Scholar 

  18. Mirkin,C. A., Letsinger,R. L., Mucic,R. C. & Storhoff,J. J. A DNA-based method for rationally assembling nanoparticles into macroscopic materials. Nature 382, 607– 609 (1996).

    Article  ADS  CAS  Google Scholar 

  19. Alivisatos,A. P. et al. Organization of ‘nanocrystal molecules’ using DNA. Nature 382, 609–611 (1996).

    Article  ADS  CAS  Google Scholar 

  20. Boal,A. K. & Rotello,V. M. Redox-modulated recognition of flavin by functionalized gold nanoparticles. J. Am. Chem. Soc. 121, 4914–4915 ( 1999).

    Article  CAS  Google Scholar 

  21. Deans,R., Ilhan,F. & Rotello,V. M. Recognition mediated unfolding of a self-assembled polymeric globule. Macromolecules 32, 4956– 4960 (1999).

    Article  ADS  CAS  Google Scholar 

  22. Park,T. K., Schroeder,J. & Rebek, J. New molecular complements to imides. Complexation to thymine derrivatives. J. Am. Chem. Soc. 113, 5125–5127 (1991).

    Article  CAS  Google Scholar 

  23. Muehldorf,A. V., Van Engen,D., Warner,J. C. & Hamilton,A. D. Aromatic aromatic interactions in molecular recognition: a family of artificial receptors for thymine that shows both face-to-face and edge-to-face interactions. J. Am. Chem. Soc. 110, 6561– 6562 (1988).

    Article  CAS  Google Scholar 

  24. 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).

  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).

    Article  CAS  Google Scholar 

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Acknowledgements

This work was supported by the NSF. V.M.R. also acknowledges support from the Petroleum Research Fund of the ACS, the Center for University Research in Polymers at the University of Massachusetts, the Alfred P. Sloan Foundation, Research Corporation, and the Camille and Henry Dreyfus Foundation.

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Authors and Affiliations

  1. Department of Chemistry,

    Andrew K. Boal, Faysal Ilhan & Vincent M. Rotello

  2. Department of Polymer Science and Engineering, University of Massachusetts, Amherst, 01003, Massachusetts , USA

    Jason E. DeRouchey, Thomas Thurn-Albrecht & Thomas P. Russell

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  1. Andrew K. Boal
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Correspondence to Vincent M. Rotello.

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Boal, A., Ilhan, F., DeRouchey, J. et al. Self-assembly of nanoparticles into structured spherical and network aggregates. Nature 404, 746–748 (2000). https://doi.org/10.1038/35008037

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