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Label-free imaging of semiconducting and metallic carbon nanotubes in cells and mice using transient absorption microscopy

Abstract

As interest in the potential biomedical applications of carbon nanotubes increases1, there is a need for methods that can image nanotubes in live cells, tissues and animals. Although techniques such as Raman2,3,4, photoacoustic5 and near-infrared photoluminescence imaging6,7,8,9,10 have been used to visualize nanotubes in biological environments, these techniques are limited because nanotubes provide only weak photoluminescence and low Raman scattering and it remains difficult to image both semiconducting and metallic nanotubes at the same time. Here, we show that transient absorption microscopy offers a label-free method to image both semiconducting and metallic single-walled carbon nanotubes in vitro and in vivo, in real time, with submicrometre resolution. By using appropriate near-infrared excitation wavelengths, we detect strong transient absorption signals with opposite phases from semiconducting and metallic nanotubes. Our method separates background signals generated by red blood cells and this allows us to follow the movement of both types of nanotubes inside cells and in the blood circulation and organs of mice without any significant damaging effects.

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Figure 1: Semiconducting and metallic nanotubes exhibit strong transient absorption signals with opposite phases.
Figure 2: Comparison of transient absorption and AFM images of the same nanotube sample show that transient absorption microscopy can detect M-SWNTs and S-SWNTs in a chirality-insensitive manner.
Figure 3: Cellular uptake and intracellular trafficking of DNA-SWNTs monitored in real time by transient absorption microscopy.
Figure 4: Imaging of RBCs and F127-wrapped SWNTs (F127-SWNTs) circulating in the blood vessels of a mouse earlobe.
Figure 5: F127-SWNTs in different organs of treated mice are visualized by transient absorption microscopy at the cellular level.

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References

  1. Liu, Z., Tabakman, S., Welsher, K. & Dai, H. Carbon nanotubes in biology and medicine: in vitro and in vivo detection, imaging and drug delivery. Nano Res. 2, 85–120 (2009).

    Article  CAS  Google Scholar 

  2. Heller, D., Baik, S., Eurell, T. & Strano, M. Single-walled carbon nanotube spectroscopy in live cells: towards long-term labels and optical sensors. Adv. Mater. 17, 2793–2799 (2005).

    Article  CAS  Google Scholar 

  3. Liu, Z. et al. Multiplexed multicolor Raman imaging of live cells with isotopically modified single walled carbon nanotubes. J. Am. Chem. Soc. 130, 13540–13541 (2008).

    Article  CAS  Google Scholar 

  4. Zavaleta, C. et al. Noninvasive Raman spectroscopy in living mice for evaluation of tumor targeting with carbon nanotubes. Nano Lett. 8, 2800–2805 (2008).

    Article  CAS  Google Scholar 

  5. De La Zerda, A. et al. Carbon nanotubes as photoacoustic molecular imaging agents in living mice. Nature Nanotech. 3, 557–562 (2008).

    Article  CAS  Google Scholar 

  6. Cherukuri, P., Bachilo, S. M., Litovsky, S. H. & Weisman, R. B. Near-infrared fluorescence microscopy of single-walled carbon nanotubes in phagocytic cells. J. Am. Chem. Soc. 126, 15638–15639 (2004).

    Article  CAS  Google Scholar 

  7. Jin, H., Heller, D. A. & Strano, M. S. Single-particle tracking of endocytosis and exocytosis of single-walled carbon nanotubes in NIH-3T3 cells. Nano Lett. 8, 1577–1585 (2008).

    Article  Google Scholar 

  8. Leeuw, T. K. et al. Single-walled carbon nanotubes in the intact organism: near-IR imaging and biocompatibility studies in drosophila. Nano Lett. 7, 2650–2654 (2007).

    Article  CAS  Google Scholar 

  9. Welsher, K. et al. A route to brightly fluorescent carbon nanotubes for near-infrared imaging in mice. Nature Nanotech. 4, 773–780 (2009).

    Article  CAS  Google Scholar 

  10. Welsher, K., Sherlock, S. P. & Dai, H. Deep-tissue anatomical imaging of mice using carbon nanotube fluorophores in the second near-infrared window. Proc. Natl Acad. Sci. USA 108, 8943–8948 (2011).

    Article  CAS  Google Scholar 

  11. O'Connell, M. J. et al. Band gap fluorescence from individual single-walled carbon nanotubes. Science 297, 593–596 (2002).

    Article  CAS  Google Scholar 

  12. Nish, A., Hwang, J-Y., Doig, J. & Nicholas, R. J. Highly selective dispersion of single-walled carbon nanotubes using aromatic polymers. Nature Nanotech. 2, 640–646 (2007).

    Article  CAS  Google Scholar 

  13. Crochet, J., Clemens, M. & Hertel, T. Quantum yield heterogeneities of aqueous single-wall carbon nanotube suspensions. J. Am. Chem. Soc. 129, 8058–8059 (2007).

    Article  CAS  Google Scholar 

  14. Ju, S-Y., Kopcha, W. P. & Papadimitrakopoulos, F. Brightly fluorescent single-walled carbon nanotubes via an oxygen-excluding surfactant organization. Science 323, 1319–1323 (2009).

    Article  CAS  Google Scholar 

  15. Kim, H., Sheps, T., Collins, P. G. & Potma, E. O. Nonlinear optical imaging of individual carbon nanotubes with four-wave-mixing microscopy. Nano Lett. 9, 2991–2995 (2009).

    Article  CAS  Google Scholar 

  16. Ye, T., Fu, D. & Warren, W. S. Nonlinear absorption microscopy. Photochem. Photobiol. 85, 631–645 (2009).

    Article  CAS  Google Scholar 

  17. Van Dijk, M. A., Lippitz, M. & Orrit, M. Detection of acoustic oscillations of single gold nanospheres by time-resolved interferometry. Phys. Rev. Lett. 95, 267406 (2005).

    Article  Google Scholar 

  18. Muskens, O. L., Del Fatti, N. & Valle, F. Femtosecond response of a single metal nanoparticle. Nano Lett. 6, 552–556 (2006).

    Article  CAS  Google Scholar 

  19. Hartland, G. V. Ultrafast studies of single semiconductor and metal nanostructures through transient absorption microscopy. Chem. Sci. 1, 303–309 (2010).

    Article  CAS  Google Scholar 

  20. Jung, Y. et al. Fast detection of the metallic state of individual single-walled carbon nanotubes using a transient-absorption optical microscope. Phys. Rev. Lett. 105, 217401 (2010).

    Article  Google Scholar 

  21. Min, W. et al. Imaging chromophores with undetectable fluorescence by stimulated emission microscopy. Nature 461, 1105–1109 (2009).

    Article  CAS  Google Scholar 

  22. Jorio, A. et al. Characterizing carbon nanotube samples with resonance Raman scattering. New J. Phys. 5, 139 (2003).

    Article  Google Scholar 

  23. Slipchenko, M. N., Le, T. T., Chen, H. & Cheng, J-X. High-speed vibrational imaging and spectral analysis of lipid bodies by compound Raman microscopy. J. Phys. Chem. B 113, 7681–7686 (2009).

    Article  CAS  Google Scholar 

  24. Roya, L., Bridget, D., Donald, B. & Ronald, R. Oligodeoxyribonucleotide association with single-walled carbon nanotubes studied by SPM. Small 3, 1912–1920 (2007).

    Article  Google Scholar 

  25. Ellingson, R. J. et al. Ultrafast photoresponse of metallic and semiconducting single-wall carbon nanotubes. Phys. Rev. B 71, 115444 (2005).

    Article  Google Scholar 

  26. Lu, S., Min, W., Chong, S., Holtom, G. R. & Xie, X. S. Label-free imaging of heme proteins with two-photon excited photothermal lens microscopy. Appl. Phys. Lett. 96, 113701 (2010).

    Article  Google Scholar 

  27. Uchiyama, K., Hibara, A., Kimura, H., Sawada, T. & Kitamori, T. Thermal lens microscope. Jpn J. Appl. Phys. 39, 5316–5322 (2000).

    Article  CAS  Google Scholar 

  28. Lauret, J. S. et al. Ultrafast carrier dynamics in single-wall carbon nanotubes. Phys. Rev. Lett. 90, 057404 (2003).

    Article  Google Scholar 

  29. Tong, L., Lu, Y., Lee, R. J. & Cheng, J-X. Imaging receptor-mediated endocytosis with a polymeric nanoparticle-based coherent anti-Stokes Raman scattering probe. J. Phys. Chem. B 111, 9980–9985 (2007).

    Article  CAS  Google Scholar 

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Acknowledgements

The authors thank Z. Zhong for providing the aligned SWNT samples, J.H. Choi for measuring the photoluminescence emission spectrum from SWNT samples, and A. Ivanisevic for assisting with AFM measurements. This work was supported by the National Science Foundation (grant no. 0828832 to J.X.C.), the Bilsland Fellowship (L.T.) and the Walther Cancer Institute and Lilly Foundation (D.E.B.).

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L.T. and J.X.C. conceived and designed the experiments. L.T. and Y.L. performed the experiments. L.T. and Y.L. analysed the data. B.D.D., Y.J., M.N.S. and D.E.B. contributed materials and analysis tools. L.T. and J.X.C. co-wrote the paper. All authors discussed the results and commented on the manuscript.

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Correspondence to Ji-Xin Cheng.

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The authors declare no competing financial interests.

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Tong, L., Liu, Y., Dolash, B. et al. Label-free imaging of semiconducting and metallic carbon nanotubes in cells and mice using transient absorption microscopy. Nature Nanotech 7, 56–61 (2012). https://doi.org/10.1038/nnano.2011.210

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