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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References
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).
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).
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).
Zavaleta, C. et al. Noninvasive Raman spectroscopy in living mice for evaluation of tumor targeting with carbon nanotubes. Nano Lett. 8, 2800–2805 (2008).
De La Zerda, A. et al. Carbon nanotubes as photoacoustic molecular imaging agents in living mice. Nature Nanotech. 3, 557–562 (2008).
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).
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).
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).
Welsher, K. et al. A route to brightly fluorescent carbon nanotubes for near-infrared imaging in mice. Nature Nanotech. 4, 773–780 (2009).
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).
O'Connell, M. J. et al. Band gap fluorescence from individual single-walled carbon nanotubes. Science 297, 593–596 (2002).
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).
Crochet, J., Clemens, M. & Hertel, T. Quantum yield heterogeneities of aqueous single-wall carbon nanotube suspensions. J. Am. Chem. Soc. 129, 8058–8059 (2007).
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).
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).
Ye, T., Fu, D. & Warren, W. S. Nonlinear absorption microscopy. Photochem. Photobiol. 85, 631–645 (2009).
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).
Muskens, O. L., Del Fatti, N. & Valle, F. Femtosecond response of a single metal nanoparticle. Nano Lett. 6, 552–556 (2006).
Hartland, G. V. Ultrafast studies of single semiconductor and metal nanostructures through transient absorption microscopy. Chem. Sci. 1, 303–309 (2010).
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).
Min, W. et al. Imaging chromophores with undetectable fluorescence by stimulated emission microscopy. Nature 461, 1105–1109 (2009).
Jorio, A. et al. Characterizing carbon nanotube samples with resonance Raman scattering. New J. Phys. 5, 139 (2003).
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).
Roya, L., Bridget, D., Donald, B. & Ronald, R. Oligodeoxyribonucleotide association with single-walled carbon nanotubes studied by SPM. Small 3, 1912–1920 (2007).
Ellingson, R. J. et al. Ultrafast photoresponse of metallic and semiconducting single-wall carbon nanotubes. Phys. Rev. B 71, 115444 (2005).
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).
Uchiyama, K., Hibara, A., Kimura, H., Sawada, T. & Kitamori, T. Thermal lens microscope. Jpn J. Appl. Phys. 39, 5316–5322 (2000).
Lauret, J. S. et al. Ultrafast carrier dynamics in single-wall carbon nanotubes. Phys. Rev. Lett. 90, 057404 (2003).
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).
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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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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DOI: https://doi.org/10.1038/nnano.2011.210
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