Abstract
Graphitic nanomaterials have unique, strong, and stable Raman vibrations that have been widely applied in chemistry and biomedicine. However, utilizing them as internal standards (ISs) to improve the accuracy of surface-enhanced Raman spectroscopy (SERS) analysis has not been attempted. Herein, we report the design of a unique IS nanostructure consisting of a large number of gold nanoparticles (AuNPs) decorated on multilayered graphitic magnetic nanocapsules (AGNs) to quantify the analyte and eliminate the problems associated with traditional ISs. The AGNs demonstrated a unique Raman band from the graphitic component, which was localized in the Raman silent region of the biomolecules, making them an ideal IS for quantitative Raman analysis without any background interference. The IS signal from the AGNs also indicated superior stability, even under harsh conditions. With the enhancement of the decorated AuNPs, the AGN nanostructures greatly improved the quantitative accuracy of SERS, in particular the exclusion of quantitative errors resulting from collection loss and non-uniform distribution of the analytes. The AGNs were further utilized for cell staining and Raman imaging, and they showed great promise for applications in biomedicine.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
Fu, D.; Zhou, J.; Zhu, W. S.; Manley, P. W.; Wang, Y. K.; Hood, T.; Wylie, A.; Xie, X. S. Imaging the intracellular distribution of tyrosine kinase inhibitors in living cells with quantitative hyperspectral stimulated Raman scattering. Nat. Chem. 2014, 6, 614–622.
Okada, M.; Smith, N. I.; Palonpon, A. F.; Endo, H.; Kawata, S.; Sodeoka, M.; Fujita, K. Label-free Raman observation of cytochrome c dynamics during apoptosis. Proc. Natl. Acad. Sci. USA 2012, 109, 28–32.
Qian, X. M.; Peng, X. H.; Ansari, D. O.; Yin-Goen, Q.; Chen, G. Z.; Shin, D. M.; Yang, L.; Young, A. N.; Wang, M. D.; Nie, S. M. In vivo tumor targeting and spectroscopic detection with surface-enhanced Raman nanoparticle tags. Nat. Biotechnol. 2008, 26, 83–90.
Abramczyk, H.; Brozek-Pluska, B. Raman imaging in biochemical and biomedical applications. Diagnosis and treatment of breast cancer. Chem. Rev. 2013, 113, 5766–5781.
Kneipp, K.; Kneipp, H.; Kneipp, J. Surface-enhanced Raman scattering in local optical fields of silver and gold nanoaggregatesfrom single-molecule Raman spectroscopy to ultrasensitive probing in live cells. Acc. Chem. Res. 2006, 39, 443–450.
Li, J. F.; Huang, Y. F.; Ding, Y.; Yang, Z. L.; Li, S. B.; Zhou, X. S.; Fan, F. R.; Zhang, W.; Zhou, Z. Y.; Wu, D. Y. et al. Shell-isolated nanoparticle-enhanced Raman spectroscopy. Nature 2010, 464, 392–395.
Bell, S. E. J.; Mackle, J. N.; Sirimuthu, N. M. S. Quantitative surface-enhanced Raman spectroscopy of dipicolinic acidtowards rapid anthrax endospore detection. Analyst 2005, 130, 545–549.
Deb, S. K.; Davis, B.; Knudsen, G. M.; Gudihal, R.; Ben- Amotz, D.; Davisson, V. J. Detection and relative quantification of proteins by surface enhanced Raman using isotopic labels. . J. Am. Chem. Soc. 2008, 130, 9624–9625.
Shen, W.; Lin, X.; Jiang, C. Y.; Li, C. Y.; Lin, H. X.; Huang, J. T.; Wang, S.; Liu, G. K.; Yan, X. M.; Zhong, Q. L. et al. Reliable quantitative SERS analysis facilitated by core–shell nanoparticles with embedded internal standards. Angew. Chem., Int. Ed. 2015, 54, 7308–7312.
Chen, Z.; Tabakman, S. M.; Goodwin, A. P.; Kattah, M. G.; Daranciang, D.; Wang, X. R.; Zhang, G. Y.; Li, X. L.; Liu, Z.; Utz, P. J. et al. Protein microarrays with carbon nanotubes as multicolor Raman labels. Nat. Biotechnol. 2008, 26, 1285–1292.
Liu, Z.; Tabakman, S.; Sherlock, S.; Li, X. L.; Chen, Z.; Jiang, K. L.; Fan, S. S.; Dai, H. J. Multiplexed five-color molecular imaging of cancer cells and tumor tissues with carbon nanotube Raman tags in the near-infrared. Nano Res. 2010, 3, 222–233.
Xu, W. G.; Ling, X.; Xiao, J. Q.; Dresselhaus, M. S.; Kong, J.; Xu, H. X.; Liu, Z. F.; Zhang, J. Surface enhanced Raman spectroscopy on a flat graphene surface. Proc. Natl. Acad. Sci. USA 2012, 109, 9281–9286.
Zheng, J.; Bai, J. H.; Zhou, Q. F.; Li, J. S.; Li, Y. H.; Yang, J. F.; Yang, R. H. DNA-templated in situ growth of AgNPs on SWNTs: A new approach for highly sensitive SERS assay of microRNA. Chem. Commun. 2015, 51, 6552–6555.
Lin, L.; Tian, X. D.; Hong, S. L.; Dai, P.; You, Q. C.; Wang, R. Y.; Feng, L. S.; Xie, C.; Tian, Z. Q.; Chen, X. Innentitelbild: A bioorthogonal Raman reporter strategy for SERS detection of glycans on live cells. Angew. Chem. 2013, 125, 7184.
Zheng, Y. Q.; Zhong, X. L.; Li, Z. Y.; Xia, Y. N. Successive, seed-mediated growth for the synthesis of single-crystal gold nanospheres with uniform diameters controlled in the range of 5-150 nm. Part. Part. Syst. Char. 2014, 31, 266–273.
Software for simulation: FDTD Solutions 8.0; Lumerical Solutions, Inc., 2015.
Chen, Y.; Chen, Z.-P.; Jin, J.-W.; Yu, R.-Q. Quantitative determination of ametryn in river water using surfaceenhanced Raman spectroscopy coupled with an advanced chemometric model. Chemom. Intell. Lab. Syst. 2015, 142, 166–171.
Cabalín, L. M.; Laserna, J. J. Fast spatially resolved surfaceenhanced Raman spectrometry on a silver coated filter paper using charge-coupled device detection. Anal. Chim. Acta 1995, 310, 337–345.
Lee, A. S. L.; Li, Y.-S. Surface-enhanced Raman spectra using silver-coated paper substrates. J. Raman Spectrosc. 1994, 25, 209–214.
Tseng, S. C.; Yu, C. C.; Wan, D. H.; Chen, H. L.; Wang, L. A.; Wu, M. C.; Su, W. F.; Han, H. C.; Chen, L. C. Eco-friendly plasmonic sensors: Using the photothermal effect to prepare metal nanoparticle-containing test papers for highly sensitive colorimetric detection. Anal. Chem. 2012, 84, 5140–5145.
Wang, J. P.; Yang, L.; Liu, B. H.; Jiang, H. H.; Liu, R. Y.; Yang, J. W.; Han, G. M.; Mei, Q. S.; Zhang, Z. P. Inkjetprinted silver nanoparticle paper detects airborne species from crystalline explosives and their ultratrace residues in open environment. Anal. Chem. 2014, 86, 3338–3345.
Yunker, P. J.; Still, T.; Lohr, M. A.; Yodh, A. G. Suppression of the coffee-ring effect by shape-dependent capillary interactions. Nature 2011, 476, 308–311.
Lasch, P. Spectral pre-processing for biomedical vibrational spectroscopy and microspectroscopic imaging. Chemom. Intell. Lab. Syst. 2012, 117, 100–114.
Author information
Authors and Affiliations
Corresponding authors
Additional information
These authors contributed equally to this work.
Electronic supplementary material
Rights and permissions
About this article
Cite this article
Zou, Y., Chen, L., Song, Z. et al. Stable and unique graphitic Raman internal standard nanocapsules for surface-enhanced Raman spectroscopy quantitative analysis. Nano Res. 9, 1418–1425 (2016). https://doi.org/10.1007/s12274-016-1037-6
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s12274-016-1037-6