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Nanogap-engineerable Raman-active nanodumbbells for single-molecule detection

Nature Materials volume 9, pages 60–67 (2010)Cite this article

Abstract

Surface-enhanced Raman scattering (SERS)-based signal amplification and detection methods using plasmonic nanostructures have been widely investigated for imaging and sensing applications. However, SERS-based molecule detection strategies have not been practically useful because there is no straightforward method to synthesize and characterize highly sensitive SERS-active nanostructures with sufficiently high yield and efficiency, which results in an extremely low cross-section area in Raman sensing. Here, we report a high-yield synthetic method for SERS-active gold–silver core–shell nanodumbbells, where the gap between two nanoparticles and the Raman-dye position and environment can be engineered on the nanoscale. Atomic-force-microscope-correlated nano-Raman measurements of individual dumbbell structures demonstrate that Raman signals can be repeatedly detected from single-DNA-tethered nanodumbbells. These programmed nanostructure fabrication and single-DNA detection strategies open avenues for the high-yield synthesis of optically active smart nanoparticles and structurally reproducible nanostructure-based single-molecule detection and bioassays.

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Figure 1: The high-yield synthetic scheme and nanogap engineering for single-DNA-tethered heterodimeric GSNDs and AFM-correlated nano-Raman spectroscopic measurement of individual GSND particles.
Figure 2: Ultraviolet–visible spectra and HRTEM images of gold monomers, gold heterodimers, gold–silver core–shell monomers and gold–silver core–shell heterodimers.
Figure 3: The AFM-correlated nano-Raman spectroscopic measurements of the synthesized nanoparticles.
Figure 4: AFM-correlated nano-Raman signals from the individual GSNDs with a 5 nm Ag shell on the same surface.
Figure 5: Single-molecule behaviours from the GSND with a 5 nm Ag shell.

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Acknowledgements

J.-M.N. was supported by the 21C Frontier Functional Proteomics Project (FPR08-A2-150), the Nano R&D programme (2008-02890) and the Basic Science Research Program (2009-0077361) through the National Research Foundation of Korea (NRF) from the Ministry of Education, Science and Technology. Y.D.S. was supported by KRICT (KK-0904-02), the Nano R&D Program (No. 2009-0082861), the Pioneer Research Center Program of NRF (No. 2009-0081511), the Development of Advanced Scientific Analysis Instrumentation Project of KRISS by MEST and the Eco-technopia 21 Project by KME. We would also like to acknowledge the Industrial Core Technology Development Program by the Ministry of Knowledge Economy (No. 10033183) for financial support.

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  1. Dong-Kwon Lim and Ki-Seok Jeon: These authors contributed equally to this work

Authors and Affiliations

  1. Department of Chemistry, Seoul National University, Seoul, 151-747, South Korea

    Dong-Kwon Lim & Jwa-Min Nam

  2. Laboratory for Advanced Molecular Probing (LAMP), NanoBio Fusion Research Center, Korea Research Institute of Chemical Technology, DaeJeon, 305-600, South Korea

    Ki-Seok Jeon, Hyung Min Kim & Yung Doug Suh

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  1. Dong-Kwon Lim
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Contributions

Y.D.S. and J.-M.N. conceived the initial idea. J.-M.N. designed synthetic schemes for nanoprobes and D.-K.L. and J.-M.N. synthesized and characterized nanoprobes. Raman spectra and AFM images were obtained by K.-S.J. and D.-K.L. under the supervision of Y.D.S. and J.-M.N. Single-molecule experiments were designed and guided by Y.D.S. and J.-M.N., and carried out by K.-S.J. and D.-K.L. H.M.K. measured and calculated the enhancement factor. J.-M.N., D.-K.L. and Y.D.S. wrote the article with partial contribution from K.-S.J. and H.M.K.

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Correspondence to Jwa-Min Nam or Yung Doug Suh.

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Lim, DK., Jeon, KS., Kim, H. et al. Nanogap-engineerable Raman-active nanodumbbells for single-molecule detection. Nature Mater 9, 60–67 (2010). https://doi.org/10.1038/nmat2596

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