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Reconfigurable 3D plasmonic metamolecules

Abstract

A reconfigurable plasmonic nanosystem combines an active plasmonic structure with a regulated physical or chemical control input. There have been considerable efforts on integration of plasmonic nanostructures with active platforms using top-down techniques. The active media include phase-transition materials, graphene, liquid crystals and carrier-modulated semiconductors, which can respond to thermal1, electrical2 and optical stimuli3,4,5. However, these plasmonic nanostructures are often restricted to two-dimensional substrates, showing desired optical response only along specific excitation directions. Alternatively, bottom-up techniques offer a new pathway to impart reconfigurability and functionality to passive systems. In particular, DNA has proven to be one of the most versatile and robust building blocks6,7,8,9 for construction of complex three-dimensional architectures with high fidelity10,11,12,13,14. Here we show the creation of reconfigurable three-dimensional plasmonic metamolecules, which execute DNA-regulated conformational changes at the nanoscale. DNA serves as both a construction material to organize plasmonic nanoparticles in three dimensions, as well as fuel for driving the metamolecules to distinct conformational states. Simultaneously, the three-dimensional plasmonic metamolecules can work as optical reporters, which transduce their conformational changes in situ into circular dichroism changes in the visible wavelength range.

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Figure 1: Reconfigurable 3D plasmonic metamolecules.
Figure 2: TEM images of the plasmonic metamolecules in the right-handed state.
Figure 3: Cycling the 3D plasmonic metamolecules between two states.
Figure 4: Cycling the 3D plasmonic metamolecules between three states.

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References

  1. Driscoll, T. et al. Memory metamaterials. Science 325, 1518–1521 (2009).

    Article  CAS  Google Scholar 

  2. Ou, J-Y., Plum, E., Zhang, J. & Zheludev, N. I. An electromechanically reconfigurable plasmonic metamaterial operating in the near-infrared. Nature Nanotech. 8, 252–255 (2013).

    Article  CAS  Google Scholar 

  3. MacDonald, K. F., Sámson, Z. L., Stockman, M. I. & Zheludev, N. I. Ultrafast active plasmonics. Nature Photon. 3, 55–58 (2009).

    Article  CAS  Google Scholar 

  4. Zhang, S. et al. Photoinduced handedness switching in terahertz chiral metamolecules. Nature Commun. 3, 942 (2012).

    Article  Google Scholar 

  5. Zheng, Y. B. et al. Active molecular plasmonics: Controlling plasmon resonances with molecular switches. Nano Lett. 9, 819–825 (2009).

    Article  CAS  Google Scholar 

  6. Seeman, N. C. DNA in a material world. Nature 421, 427–431 (2003).

    Article  Google Scholar 

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

    Article  CAS  Google Scholar 

  8. Krishnan, Y. & Simmel, F. C. Nucleic acid based molecular devices. Angew. Chem. Int. Ed. 50, 3124–3156 (2011).

    Article  CAS  Google Scholar 

  9. Yurke, B., Turberfield, A. J., Mills, A. P., Simmel, F. C. & Neumann, J. L. A DNA-fuelled molecular machine made of DNA. Nature 406, 605–608 (2000).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  11. Andersen, E. S. et al. Self-assembly of a nanoscale DNA box with a controllable lid. Nature 459, 73–76 (2009).

    Article  CAS  Google Scholar 

  12. Ke, Y., Ong, L. L., Shih, W. M. & Yin, P. Three-dimensional structures self-assembled from DNA bricks. Science 338, 1177–1183 (2012).

    Article  CAS  Google Scholar 

  13. Castro, C. E. et al. A primer to scaffolded DNA origami. Nature Methods 8, 221–229 (2011).

    Article  CAS  Google Scholar 

  14. Kuzyk, A. et al. DNA-based self-assembly of chiral plasmonic nanostructures with tailored optical response. Nature 483, 311–314 (2012).

    Article  CAS  Google Scholar 

  15. Fasman, G. D. Circular Dichroism and the Conformational Analysis of Biomolecules (Plenum, 1996).

    Book  Google Scholar 

  16. Wang, H., Brandl, D. W., Nordlander, P. & Halas, N. J. Plasmonic nanostructures: Artificial molecules. Acc. Chem. Res. 40, 53–62 (2007).

    Article  Google Scholar 

  17. Holliday, R. A mechanism for gene conversion in fungi. Genet. Res. 5, 282–304 (1964).

    Article  Google Scholar 

  18. 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 

  19. Auguié, B., Alonso-Gómez, J. L., Guerrero-Martínez, A. & Liz-Marzán, L. M. Fingers crossed: Optical activity of a chiral dimer of plasmonic nanorods. J. Phys. Chem. Lett. 2, 846–851 (2011).

    Article  Google Scholar 

  20. Lan, X. et al. Bifacial DNA origami-directed discrete, three-dimensional, anisotropic plasmonic nanoarchitectures with tailored optical chirality. J. Am. Chem. Soc. 135, 11441–11444 (2013).

    Article  CAS  Google Scholar 

  21. Zhao, Y., Belkin, M. A. & Alù, A. Twisted optical metamaterials for planarized ultrathin broadband circular polarizers. Nature Commun. 3, 870 (2012).

    Article  CAS  Google Scholar 

  22. Ma, W. et al. Chiral plasmonics of self-assembled nanorod dimers. Sci. Rep. 3, 1934 (2013).

    Article  Google Scholar 

  23. Zhang, D. Y. & Seelig, G. Dynamic DNA nanotechnology using strand-displacement reactions. Nature Chem. 3, 103–113 (2011).

    Article  CAS  Google Scholar 

  24. Graugnard, E. et al. DNA-controlled excitonic switches. Nano Lett. 12, 2117 (2012).

    Article  CAS  Google Scholar 

  25. Ma, W. et al. Attomolar DNA detection with chiral nanorod assemblies. Nature Commun. 4, 2689 (2013).

    Article  Google Scholar 

  26. Draine, B. T. & Flatau, P. J. Discrete-dipole approximation for scattering calculations. J. Opt. Soc. Am. 11, 1491–1499 (1994).

    Article  Google Scholar 

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

    Article  CAS  Google Scholar 

  28. Johnson, P. B. & Christy, R. W. Optical constants of the noble metals. Phys. Rev. B 6, 4370–4379 (1972).

    Article  CAS  Google Scholar 

  29. Liu, N., Hentschel, M., Weiss, T., Alivisatos, A. P. & Giessen, H. Three-dimensional plasmon rulers. Science 332, 1407–1410 (2011).

    Article  CAS  Google Scholar 

  30. Sönnichsen, C., Reinhard, B. M., Liphardt, J. & Alivisatos, A. P. A molecular ruler based on plasmon coupling of single gold and silver nanoparticles. Nature Biotechnol. 23, 741–745 (2005).

    Article  Google Scholar 

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

    Article  CAS  Google Scholar 

  32. Zhang, S. et al. Negative refractive index in chiral metamaterials. Phys. Rev. Lett. 102, 023901 (2009).

    Article  Google Scholar 

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Acknowledgements

We thank A. Jeltsch and R. Jurkowska for assistance with CD spectrometry. We thank M. Kelsch and H. Ries for assistance with TEM microscopy and DNA scaffold preparation, respectively. We acknowledge S. Hein for material visualizations and F. Simmel for advice, respectively. TEM data were collected at the Stuttgart Center for Electron Microscopy (StEM). N.L. was supported by the Sofja Kovalevskaja Award from the Alexander von Humboldt-Foundation. A.K. was supported by a postdoctoral fellowship from the Alexander von Humboldt-Foundation. A.K. and N.L. were supported by a Marie Curie CIG Fellowship and the Grassroots Proposal M10330 from the Max Planck Institute for Intelligent Systems. T.L. and R.S. were supported by the Volkswagen Foundation and the DFG cluster of excellence NIM. H.Z. and A.O.G. were supported by the US Army Research Office under grant number W911NF-12-1-0407 and by Volkswagen Foundation (Germany). Use of the Computing Cluster at the Center for Nanoscale Materials was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.

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A.K., T.L. and N.L. conceived the experiments. A.K. and R.S. designed the DNA origami nanostructures. A.K. performed the experiments. H.Z. and A.O.G. carried out the theoretical calculations. A.K. and N.L. wrote the manuscript. All authors discussed the results, analysed the data and commented on the manuscript.

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Correspondence to Anton Kuzyk or Na Liu.

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The authors declare no competing financial interests.

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Kuzyk, A., Schreiber, R., Zhang, H. et al. Reconfigurable 3D plasmonic metamolecules. Nature Mater 13, 862–866 (2014). https://doi.org/10.1038/nmat4031

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