Ultrasensitive Detection of Polycyclic Aromatic Hydrocarbons (PAHs) in Water Using Three-Dimensional SERS Substrate Based on Porous Material and pH 13 Gold Nanoparticles
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Sensitivity is crucially important for surface-enhanced Raman spectroscopy (SERS) application to detect trace-level polycyclic aromatic hydrocarbons (PAHs) in the seawater. In this study, a high sensitivity three-dimensional (3-D) SERS substrate composed with syringe filter, glycidyl methacrylate-ethylene dimethacrylate (GMA-EDMA) porous material and optimal parameters (57 nm, pH 13) gold nanoparticles (AuNPs) was developed for the detection of PAHs in water. The enhancement effect and repeatability of this 3-D substrate were also explored. The Raman intensity of pyrene using 3-D SERS substrate is about 8 times higher than that of substrate only using pH 13 gold colloid solution and about 12 times higher than that of substrate using natural AuNPs and GMA-EDMA porous material, which means both the pH 13 AuNPs and the GMA-EDMA porous material are important factors for the sensitivity of this 3-D SERS substrate. Good repeatability of this optimal 3-D substrate was obtained. The relative standard deviation (RSD) is less than 8.66% on the same substrate and less than 3.69% on other different substrates. Four kinds of PAHs, i.e., phenanthrene, pyrene, benzo(a)pyrene, benzo(k)fluoranthene and their mixture, were detected at the different concentrations. Their limits of detection (LODs) are 8.3×10−10 (phenanthrene), 2.1×10−10 (pyrene), 3.8×10−10 (benzo(a)pyrene) and 1.7×10−10mol L−1 (benzo (k)fluoranthene), respectively. In addition, these four PAHs were also detected by fluorescence spectroscopy to evaluate the sensitivity of SERS technology using this optimal 3-D SERS substrate. The results showed that the sensitivity of SERS based on the 3-D SERS substrate even using the portable Raman system was closed to that of fluorescence spectroscopy. Therefore, the SERS technology using this optimal 3-D substrate is expected to be an in-situ method for the detection of environmental PAHs.
Key wordssurface-enhanced Raman scattering (SERS) polycyclic aromatic hydrocarbons (PAHs) three-dimensional SERS substrate fluorescence spectroscopy
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This research was supported by the National Natural Science Foundation of China (No. 41476081), the Major Research and Development Project in Shandong Province (Nos. 2016GSF115020, 2019GHY112027) and the Shandong Provincial Natural Science Foundation (No. ZR2015DM007).
- Chiang, H. P., Mou, B., Li, K. P., Chiang, P., Wang, D., Lin, S. J., and Tse, W. S., 2015. FT-Raman, FT-IR and normal-mode analysis of carcinogenic polycyclic aromatic hydrocarbons. Part I-A density functional theory study of benzo (a) pyrene (BaP) and benzo (e) pyrene (BeP). Journal of Raman Spectroscopy, 32 (1): 45–51.CrossRefGoogle Scholar
- Dribek, M., Rinnert, E., Colas, F., Crassous, M. P., Thioune, N., David, C., Chapelle, M., and Compére, C., 2014. Organometallic nanoprobe to enhance optical response on the polycyclic aromatic hydrocarbon benzo [a] pyrene immunoassay using SERS technology. Environmental Science and Pollution Research, 24 (35): 27070–27076, DOI: https://doi.org/10.1007/s11356-014-3384-8.CrossRefGoogle Scholar
- Frank, O., Jehlička, J., and Edwards, H. G. M., 2007. Raman spectroscopy as tool for the characterization of thio-polyaromatic hydrocarbons in organic minerals. Spectrochimica Acta Part A-Molecular and Biomolecular Spectroscopy, 68 (4): 1065–1069, DOI: https://doi.org/10.1016/j.saa.2006.12.033.CrossRefGoogle Scholar
- Hu, J., Fang, Q., Sheng, R. S., Xu, Z. S., and Zeng, Y. E., 2000. Surface-enhanced Raman spectroscopy of biliverdin. Acta Laser Biology Sinica, 9 (3): 221–227, DOI: https://doi.org/10.3969/j.issn.1007-7146.2000.03.016.Google Scholar
- Kubackova, J., Fabriciova, G., Miskovsky, P., Jancura, D., and Sanchezcortes, S., 2014. Sensitive surface-enhanced raman spectroscopy (SERS) detection of organochlorine pesticides by alkyl dithiol-functionalized metal nanoparticles-induced plasmonic hot spots. Analytical Chemistry, 87 (1): 663–669, DOI: https://doi.org/10.1021/ac503672f.CrossRefGoogle Scholar
- Kwon, Y. H., Kolomijeca, A., Sowoidnich, K., and Kronfeldt, H. D., 2011. High sensitivity calixarene SERS substrates for the continuous in-situ detection of PAHs in seawater. SPIE Defense, Security, and Sensing, Orlando, Florida, USA, IV, 525–529.Google Scholar
- Li, D. F., Cao, B., Yang, G., Li, Z. W., Gao, S. Q., Zhou, M. M, Men, Z. W., and Zhang, X. Y., 2009. Effect of pH value in silver colloids system on surface-enhanced Raman scattering spectroscopy of crystal violet. The Journal of Light Scattering, 21 (2): 132–135, DOI: https://doi.org/10.13883/j.issn1004-5929.2009.02.006 (in Chinese with English abstract).Google Scholar
- Olson, L. G., Uibel, R. H., and Harris, J. M., 2004. C18-modified metal-colloid substrates for surface-enhanced Raman detection of trace-level polycyclic aromatic hydrocarbons in aqueous solution. Applied Spectrocopy, 58 (12): 1394–1400, DOI: https://doi.org/10.1366/0003702042641380.CrossRefGoogle Scholar
- Pfannkuche, J., Lubecki, L., Schmidt, H., Kowalewska, G., and Kronfeldt, H. D., 2012. The use of surface-enhanced Raman scattering (SERS) for detection of PAHs in the Gulf of Gdańsk (Baltic Sea). Marine Pollution Bulletin, 64 (3): 614–626, DOI: https://doi.org/10.1016/j.marpolbul.2011.12.008.CrossRefGoogle Scholar
- Shi, X. F., Liu, S., Han, X. H., Ma, J., Jiang, Y. C., and Yu, G. F., 2015. High-sensitivity surface-enhanced Raman scattering (SERS) substrate based on a gold colloid solution with a pH change for detection of trace-level polycyclic aromatic hydrocarbons in aqueous solution. Applied Spectroscopy, 69: 574–579, DOI: https://doi.org/10.1366/14-07614R.CrossRefGoogle Scholar
- Shinohara, H., Yamakita, Y., and Ohno, K., 1998. Raman spectra of polycyclic aromatic hydrocarbons. Comparison of calculated Raman intensity distributions with observed spectra for naphthalene, anthracene, pyrene, and perylene. Journal of Molecular Structure, 442 (1–3): 221–234, DOI: https://doi.org/10.1016/S0022-2860(97)00335-9.CrossRefGoogle Scholar
- Thomsen, V., Schatzlein, D., and Mercuro, D., 2003. Limits of detection in spectroscopy. Spectroscopy, 18 (12): 112–114.Google Scholar
- Wang, X., Hao, W., Zhang, H., Pan, Y., Kang, Y., Zhang, X., Zou, M., Tong, P., and Du, Y., 2015. Analysis of polycyclic aromatic hydrocarbons in water with gold nanoparticles decorated hydrophobic porous polymer as surface-enhanced Raman spectroscopy substrate. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 139: 214–221, DOI: https://doi.org/10.1016/j.saa.2014.11.104.CrossRefGoogle Scholar