Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

DNA-based self-assembly of chiral plasmonic nanostructures with tailored optical response

Abstract

Matter structured on a length scale comparable to or smaller than the wavelength of light can exhibit unusual optical properties1. Particularly promising components for such materials are metal nanostructures, where structural alterations provide a straightforward means of tailoring their surface plasmon resonances and hence their interaction with light2,3. But the top-down fabrication of plasmonic materials with controlled optical responses in the visible spectral range remains challenging, because lithographic methods are limited in resolution and in their ability to generate genuinely three-dimensional architectures4,5. Molecular self-assembly6,7 provides an alternative bottom-up fabrication route not restricted by these limitations, and DNA- and peptide-directed assembly have proved to be viable methods for the controlled arrangement of metal nanoparticles in complex and also chiral geometries8,9,10,11,12,13,14. Here we show that DNA origami15,16 enables the high-yield production of plasmonic structures that contain nanoparticles arranged in nanometre-scale helices. We find, in agreement with theoretical predictions17, that the structures in solution exhibit defined circular dichroism and optical rotatory dispersion effects at visible wavelengths that originate from the collective plasmon–plasmon interactions of the nanoparticles positioned with an accuracy better than two nanometres. Circular dichroism effects in the visible part of the spectrum have been achieved by exploiting the chiral morphology of organic molecules and the plasmonic properties of nanoparticles18,19,20, or even without precise control over the spatial configuration of the nanoparticles12,21,22. In contrast, the optical response of our nanoparticle assemblies is rationally designed and tunable in handedness, colour and intensity—in accordance with our theoretical model.

This is a preview of subscription content, access via your institution

Access options

Rent or buy this article

Prices vary by article type

from$1.95

to$39.95

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Assembly of DNA origami gold nanoparticle helices and principle of circular dichroism.
Figure 2: Circular dichroism of self-assembled gold nanohelices.
Figure 3: Spectral tuning of circular dichroism by metal composition.
Figure 4: Optical rotatory dispersion of self-assembled gold nanohelices.

References

  1. Liu, Y. & Zhang, X. Metamaterials: a new frontier of science and technology. Chem. Soc. Rev. 40, 2494–2507 (2011)

    Article  CAS  Google Scholar 

  2. Barnes, W. L., Dereux, A. & Ebbesen, T. W. Surface plasmon subwavelength optics. Nature 424, 824–830 (2003)

    Article  ADS  CAS  Google Scholar 

  3. Polman, A. Plasmonics applied. Science 322, 868–869 (2008)

    Article  Google Scholar 

  4. Soukoulis, C. M. & Wegener, M. Past achievements and future challenges in the development of three-dimensional photonic metamaterials. Nature Photon. 5, 523–530 (2011)

    Article  ADS  CAS  Google Scholar 

  5. Gansel, J. K. et al. Gold helix photonic metamaterial as broadband circular polarizer. Science 325, 1513–1515 (2009)

    Article  ADS  CAS  Google Scholar 

  6. Jones, M. R., Osberg, K. D., Macfarlane, R. J., Langille, M. R. & Mirkin, C. A. Templated techniques for the synthesis and assembly of plasmonic nanostructures. Chem. Rev. 111, 3736–3827 (2011)

    Article  CAS  Google Scholar 

  7. Fan, J. A. et al. Self-assembled plasmonic nanoparticle clusters. Science 328, 1135–1138 (2010)

    Article  ADS  CAS  Google Scholar 

  8. Seeman, N. C. Nanomaterials based on DNA. Annu. Rev. Biochem. 79, 65–87 (2010)

    Article  CAS  Google Scholar 

  9. Tan, S. J., Campolongo, M. J., Luo, D. & Cheng, W. Building plasmonic nanostructures with DNA. Nature Nanotechnol. 6, 268–276 (2011)

    Article  ADS  CAS  Google Scholar 

  10. Ding, B. et al. Gold nanoparticle self-similar chain structure organized by DNA origami. J. Am. Chem. Soc. 132, 3248–3249 (2010)

    Article  CAS  Google Scholar 

  11. Mastroianni, A. J., Claridge, S. A. & Alivisatos, A. P. Pyramidal and chiral groupings of gold nanocrystals assembled using DNA scaffolds. J. Am. Chem. Soc. 131, 8455–8459 (2009)

    Article  CAS  Google Scholar 

  12. Chen, W. et al. Nanoparticle superstructures made by polymerase chain reaction: collective interactions of nanoparticles and a new principle for chiral materials. Nano Lett. 9, 2153–2159 (2009)

    Article  ADS  CAS  Google Scholar 

  13. Sharma, J. et al. Control of self-assembly of DNA tubules through integration of gold nanoparticles. Science 323, 112–116 (2009)

    Article  ADS  CAS  Google Scholar 

  14. Chen, C.-L. & Rosi, N. L. Preparation of unique 1-D nanoparticle superstructures and tailoring their structural features. J. Am. Chem. Soc. 132, 6902–6903 (2010)

    Article  CAS  Google Scholar 

  15. Rothemund, P. W. K. Folding DNA to create nanoscale shapes and patterns. Nature 440, 297–302 (2006)

    Article  ADS  CAS  Google Scholar 

  16. Douglas, S. M. et al. Self-assembly of DNA into nanoscale three-dimensional shapes. Nature 459, 414–418 (2009)

    Article  ADS  CAS  Google Scholar 

  17. Fan, Z. & Govorov, A. O. Plasmonic circular dichroism of chiral metal nanoparticle assemblies. Nano Lett. 10, 2580–2587 (2010)

    Article  ADS  CAS  Google Scholar 

  18. Schaaff, T. G. & Whetten, R. L. Giant gold−glutathione cluster compounds: intense optical activity in metal-based transitions. J. Phys. Chem. B 104, 2630–2641 (2000)

    Article  CAS  Google Scholar 

  19. Shemer, G. et al. Chirality of silver nanoparticles synthesized on DNA. J. Am. Chem. Soc. 128, 11006–11007 (2006)

    Article  CAS  Google Scholar 

  20. George, J. & Thomas, K. G. Surface plasmon coupled circular dichroism of Au nanoparticles on peptide nanotubes. J. Am. Chem. Soc. 132, 2502–2503 (2010)

    Article  CAS  Google Scholar 

  21. Guerrero-Martínez, A. et al. Intense optical activity from three-dimensional chiral ordering of plasmonic nanoantennas. Angew. Chem. Int. Edn Engl. 50, 5499–5503 (2011)

    Article  Google Scholar 

  22. Guerrero-Martínez, A., Alonso-Gómez, J. L., Auguié, B., Cid, M. M. & Liz-Marzán, L. M. From individual to collective chirality in metal nanoparticles. NanoToday 6, 381–400 (2011)

    Article  Google Scholar 

  23. Berova, N., Nakanishi, K. & Woody, R. W. Circular Dichroism: Principles and Applications 2nd edn (Wiley-VCH, 2000)

    Google Scholar 

  24. Tørring, T., Voigt, N. V., Nangreave, J., Yan, H. & Gothelf, K. V. DNA origami: a quantum leap for self-assembly of complex structures. Chem. Soc. Rev. 40, 5636–5646 (2011)

    Article  Google Scholar 

  25. Fan, Z. & Govorov, A. O. Helical metal nanoparticle assemblies with defects: plasmonic chirality and circular dichroism. J. Phys. Chem. C 115, 13254–13261 (2011)

    Article  CAS  Google Scholar 

  26. Schreiber, R. et al. DNA origami-templated growth of arbitrarily shaped metal nanoparticles. Small 7, 1795–1799 (2011)

    Article  CAS  Google Scholar 

  27. Pilo-Pais, M., Goldberg, S., Samano, E., LaBean, T. H. & Finkelstein, G. Connecting the nanodots: programmable nanofabrication of fused metal shapes on DNA templates. Nano Lett. 11, 3489–3492 (2011)

    Article  ADS  CAS  Google Scholar 

  28. Halas, N. J., Lal, S., Chang, W.-S., Link, S. & Nordlander, P. Plasmons in strongly coupled metallic nanostructures. Chem. Rev. 111, 3913–3961 (2011)

    Article  CAS  Google Scholar 

  29. Urzhumov, Y. A. et al. Plasmonic nanoclusters: a path towards negative-index metafluids. Opt. Express 15, 14129–14145 (2007)

    Article  ADS  Google Scholar 

  30. Pendry, J. B. A chiral route to negative refraction. Science 306, 1353–1355 (2004)

    Article  ADS  CAS  Google Scholar 

Download references

Acknowledgements

We thank H. Dietz and G. Acuna for experimental advice and B. Yurke, E. Graugnard, J. O. Rädler and J. P. Kotthaus for discussions. We acknowledge J. Buchner and M. Rief for giving us access to their CD spectrometers, E. Herold for help with the CD measurements, and T. Martin and S. Kempter for assistance. We also thank D. M. Smith for carefully reading the manuscript. This work was funded by the Volkswagen Foundation, the DFG Cluster of Excellence NIM (Nanosystems Initiative Munich) and the NSF (USA).

Author information

Authors and Affiliations

Authors

Contributions

A.K., R.S., A.H., F.C.S., A.O.G. and T.L. designed the research. A.K., R.S. and E.-M.R. designed the nanostructures and performed CD measurements. G.P. produced and purified gold samples. A.H. and T.L. investigated ORD effects. Z.F. and A.O.G. performed theoretical calculations. A.K., R.S. and A.O.G. prepared the figures and A.K., R.S., A.H., F.C.S., A.O.G. and T.L. wrote the manuscript.

Corresponding author

Correspondence to Tim Liedl.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

The file contains Supplementary Notes 1-10, which include Supplementary Theory, Supplementary Methods, Supplementary Data, Supplementary Figures 1-30 and Supplementary References. (PDF 5859 kb)

Supplementary Movie

The movie shows optical rotatory dispersion of dried nanohelices. The samples and set-up investigated here are also described in Supplementary Figure 26 – see Supplementary Information file. (MOV 5493 kb)

PowerPoint slides

Rights and permissions

Reprints and permissions

About this article

Cite this article

Kuzyk, A., Schreiber, R., Fan, Z. et al. DNA-based self-assembly of chiral plasmonic nanostructures with tailored optical response. Nature 483, 311–314 (2012). https://doi.org/10.1038/nature10889

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nature10889

This article is cited by

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing