Abstract
Neuroendocrine tumors, such as pheochromocytoma or paraganglioma, are dangerous tumors that constitute a potential threat for a large number of patients. Currently, the biochemical diagnosis of neuroendocrine tumors is based on measurement of the direct secretory products of the adrenomedullary-sympathetic system or of their metabolites, such as catecholamines or their metanephrine derivatives, from plasma or urine. The techniques used for analysis of plasma free metanephrines, i.e. high-performance liquid chromatography or high-performance liquid chromatography coupled with mass-spectrometry are technically-demanding and time consuming, which limit their availability. Here we demonstrate a simple, fast and low-cost method for detecting metanephrine by Surface Enhanced Raman Scattering (SERS). The protocol consists in using evaporation-induced self-assembly of gold (Au) nanoparticles incubated with the analyte, on planar gold films. The assembly process produces regions with a dense distribution of both inter-particle gaps and particle-film gaps. Finite-difference time-domain simulations confirm that both kinds of gaps are locations of enhanced electromagnetic fields resulting from inter-particle and particle-film plasmonic coupling, useful for SERS amplification. Metanephrine vibrational bands assignment was performed according to density functional theory calculations. Metanephrine metabolite was detected in liquid at concentration levels lower than previously reported for other similar metabolites. The obtained results demonstrate that the Au nanoparticle/Au film exhibits noticeable SERS amplification of the adsorbed metabolite and can be used in the design of efficient, stable SERS-active substrates for the detection and identification of specific tumor markers.
Abbreviations
- HPLC:
-
High-performance liquid chromatography
- SERS:
-
Surface Enhanced Raman Scattering
- FDTD:
-
Finite-difference time-domain simulations
- DFT:
-
Density functional theory
- ELISA:
-
Enzyme-linked immunosorbent assay
- AFM:
-
Atomic force microscopy
- AuNPs:
-
Gold nanoparticles
- TEM:
-
Transmission Electron Microscopy
References
A. M. Alam, M. Kamruzzaman, S. H. Lee, Y. H. Kim, S. Y. Kim, G. M. Kim, H. J. Jo, S. H. Kim, Microchim Acta 176, 153 (2012)
N. F. Atta, A. Galal, E. H. El-Ads, Analyst 137, 2658 (2012)
M. Baia, S. Astilean, T. Iliescu, Springer Berlin Heidelberg, (2008)
A. D. Becke, Phys Rev A 38, 3098 (1988)
A. D. Becke, J Chem Phys 98, 1372 (1993)
S. C. Boca, C. Farcau, S. Astilean, Nucl Inst Methods Phys Res B 267, 406 (2009)
A. Bouvrée, A. D. Orlando, T. Makiabadi, S. Martin, G. Louarn, J. Y. Mevellec, B. Humbert, Gold Bull 46, 283 (2013)
J. G. Boyle, D. F. Davidson, C. G. Perry, J. M. C. Connell, J Clin Endocrinol Metab 92, 4602 (2007)
G. Braun, S. J. Lee, M. Dante, T. Q. Nguyen, M. Moskovits, N. Reich, J Am Chem Soc 129, 6378 (2007)
T. Chung, S. Y. Lee, E. Y. Song, H. Chun, B. Lee, Sensors 11, 10907 (2011)
J. D. Driskell, R. J. Lipert, M. D. Porter, J Phys Chem B 110, 17444 (2006)
C. L. Du, C. J. Du, Y. M. You, C. J. He, J. Luo, D. N. Shi, Plasmonics 7, 475 (2012)
G. Eisenhofer, M. Walther, H. R. Keiser, J. W. M. Lenders, P. Friberg, K. Pacak, Braz J Med Biol Res 33, 1157 (2000)
C. Farcau, S. Astilean, J Mol Struct 1073, 102 (2014)
G. Frens, Nat Phys Sci 241, 20 (1973)
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, et al., Gaussian 03, Revision E.01-SMP (Gaussian, Inc., Pittsburgh PA, 2003)
V. Gardet, B. Gatta, G. Simonnet, A. Tabarin, G. Chêne, D. Ducassou, J. B. Corcuff, J Hypertens 19, 1029 (2001)
E. Gerlo, C. Sevens, Ann Surg 243, 102 (1994)
E. A. Gerlo, C. Sevens, Clin Chem 40, 250 (2006)
C. Girard, E. Dujardin, G. Baffou, R. Quidant, New J Phys 10, 105016 (2008)
J. Hallet, C. H. Law, M. Cukier, R. Saskin, N. Liu, S. Singh, Cancer 121, 589 (2015)
V. M. Hallmark, A. Campion, J. Chem. Phys. 84, 2933 (1986)
X. He, J. Gabler, C. Yuan, S. Wang, Y. Shi, M. Kozak, J Chromatogr B Anal Technol Biomed Life Sci 879, 2355 (2011)
X. Hu, T. Wang, L. Wang, S. Dong, J Phys Chem C 111, 6962 (2007)
H. Hwang, H. Chon, J. Choo, J. K. Park, Anal Chem 82, 7603 (2010)
I. Ilias, K. Pacak, J Clin Endocrinol Metab 89, 479 (2004)
K. Jeyaraman, V. Natarajan, N. Thomas, P. M. Jacob, A. Nair, N. Shanthly, R. Oommen, G. Varghese, F. J. Joseph, M. S. Seshadri, S. Rajaratnam, Ind J Med Res 137, 316 (2013)
W. F. J. Young, Eur. J Endourol 136, 28 (1997)
K. Kneipp, M. Moskovits, H. Kneipp, Springer Berlin Heidelberg, (2006)
I. A. Larmour, D. Graham, Analyst 136, 3831 (2011)
N. S. Lee, Y. Z. Hsieh, R. F. Paisley, M. D. Morris, Anal Chem 60, 442 (1988)
J. W. Lenders, G. Eisenhofer, M. Mannelli, K. Pacak, Lancet 366, 665 (2005)
J. W. Lenders, H. R. Keiser, D. S. Goldstein, J. J. Willemsen, P. Friberg, M. C. Jacobs, P. W. Kloppenborg, T. Thien, G. Eisenhofer, Ann Intern Med 123, 101 (1995)
J. W. Lenders, K. Pacak, M. W. McClellan, W. M. Linehan, M. Mannelli, P. Friberg, H. R. Keiser, D. S. Goldstein, G. Eisenhofer, J Am Med Assoc 287, 1427 (2002)
N. C. Lindquist, P. Nagpal, K. M. McPeak, D. J. Norris, S. H. Oh, Rep Prog Phys 75, 036501 (2012)
M. Moskovits, J. S. Suh, J Phys Chem 88, 5526 (1984)
C. Mu, Q. Zhang, D. Wu, Y. Zhang, Q. Zhang, Biomed Chromatogr 29, 148 (2015)
C. H. Munro, W. E. Smith, M. Garner, J. Clarkson, P. C. White, Langmuir 11, 3712 (1995)
C. J. Orendorff, A. Gole, T. K. Sau, C. J. Murphy, Anal Chem 77, 3261 (2005)
M. K. Par, Bull Kor Chem Soc 13, 230 (1992)
W. H. Park, S. H. Ahn, Z. H. Kim, ChemPhysChem 9, 2491 (2008)
J. P. Perdew, Y. Wang, Phys Rev B 45, 13244 (1992)
N. M. B. Perney, J. J. Baumberg, M. E. Zoorob, M. D. B. Charlton, S. Mahnkopf, C. M. Netti, Opt Express 14, 847 (2006)
C. G. Perry, A. M. Sawka, R. Singh, L. Thabane, J. Bajnarek, W. F. J. Young, Clin Endocrinol 66, 703 (2007)
M. Procopiou, H. Finney, S. A. Akker, S. L. Chew, W. M. Drake, J. Burrin, A. B. Grossman, Eur J Endocrinol 161, 131 (2009)
W. Raber, W. Raffesberg, M. Bischof, C. Scheuba, B. Niederle, S. Gasic, W. Waldhäus, M. Roden, Arch Intern Med 160, 2957 (2000)
G. Rauhut, P. J. Pulay, Phys Chem 99, 3093 (1995)
E. Ringe, M. R. Langille, K. Sohn, J. Zhang, J. Huang, C. A. Mirkin, R. P. Van Duyne, L. D. Marks, J Phys Chem Lett 3, 1479 (2012)
A. M. Sawka, R. Jaeschke, R. J. Singh, W. F. Jr, Young, J. Clin Endocrinol Metab 88, 553 (2003)
B. G. Taal, O. Visser, Neuroendocrinology 80(Suppl 1), 3 (2004)
J. Turkevich, P. C. Stevenson, J. Hillier, Discuss Faraday Soc 11, 55 (1951)
N. Unger, C. Pitt, I. L. Schmidt, M. K. Walz, K. W. Schmid, T. Philipp, K. Mann, S. Petersenn, Eur J Endocrinol 154, 409 (2003)
W. Wang, Y. Yin, Z. Tana, J. Liu, Nanoscale 6, 9588 (2014)
J. Yang, X. Tan, W.-C. Shih, M. M.-C. Cheng, Biomed Microdevices 16, 673 (2014)
X. Ye, L. Qi, Nano Today 6, 608 (2011)
H. Yuan, K. P. F. Janssen, T. Franklin, G. Lu, L. Su, X. Gu, H. Uji, M. B. J. Roeffaersab, J. Hofkens, RSC Adv 5, 6829 (2015)
Z. Zhu, T. Zhu, Z. Liu, Nanotechnology 15, 357 (2004)
Acknowledgment
This work was supported by Babes-Bolyai University, Cluj-Napoca, Romania under the Research Grant for Young Scientists, Contract GTC-UBB No. 34056/2013. S. Boca acknowledges post-doctoral grant of the Romanian Ministry of Education, CNCS-UEFISCDI, Project number PN-II-RU-PD-2012-3-0111. M. Baia acknowledges COST action BM1401.
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ESM 1
Nanoparticle size distribution by dynamic light scattering (DLS), extinction spectra of colloidal gold nanoparticles mixed with various concentrations of metanephrine, SERS spectra of metanephrine in aged colloid, optical images of circular deposit made by gold nanoparticles on gold film. (DOCX 1130 kb)
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Boca, S., Farcau, C., Baia, M. et al. Metanephrine neuroendocrine tumor marker detection by SERS using Au nanoparticle/Au film sandwich architecture. Biomed Microdevices 18, 12 (2016). https://doi.org/10.1007/s10544-016-0037-3
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DOI: https://doi.org/10.1007/s10544-016-0037-3