Silver Anchored α-MnO2 Nanorods Based SERS Substrates for Salivary Thiocyanate Detection and Application in Oral Cancer Diagnosis

Navami Sunil
PSG institute of Advanced Studies, Coimbatore, India

Rajesh Unnathpadi
PSG institute of Advanced Studies, Coimbatore, India

Biji Pullithadathil (Login required)
PSG institute of Advanced Studies, Coimbatore, India

Paper #7203 received 21 Feb 2023; revised manuscript received 19 Apr 2023; accepted for publication 24 Jun 2023; published online 31 Aug 2023.


Salivary sensors are ideal non-invasive diagnostic platforms for cancer detection owing to the existence of many proteins and metabolites that can reflect individual’s health status. Elevated levels of thiocyanate ( ) in smokers’ saliva may be a potential biomarker indicating increased oral cancer risk due to the nitrosation process. Herein, we report a highly sensitive,
label-free, ultrasensitive surface-enhanced Raman spectroscopy (SERS) detection of salivary thiocyanate using silver anchored α-MnO2 nanorods based SERS substrates for the early detection of oral cancer. The structural and morphological characterization of the synthesised Ag/ α-MnO2 nanorods have been performed using XRD, FTIR, and TEM analysis. The intensity of SERS peak at around 2170 cm−1, originating from the −C≡N stretching mode, indicated the concentrations of SCN ions. The SERS spectra of  was recorded at concentrations ranging from 1 to 6 mM, which was utilised to differentiate between smokers and non-smokers and hence to predict the risk of oral cancer. 


salivary sensors; non-invasive diagnosis; oral cancer; surface enhanced Raman spectroscopy; thiocyanate

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1. M. Kumar, R. Nanavati, T. G. Modi, and C. Dobariya, “Oral cancer: Etiology and risk factors: A review,” Journal of Cancer Research and Therapeutics 12(2), 458–463 (2016).

2. M. T. Ashby, A. C. Carlson, and M. J. Scott, “Redox buffering of hypochlorous acid by thiocyanate in physiologic fluids,” Journal of the American Chemical Society 126(49), 15976–15977 (2004).

3. A. Madiyal, V. Ajila, S. G. Babu, S. Hegde, S. Kumari, M. Madi, S. Achalli, P. Alva, and H. Ullal, “Status of thiocyanate levels in the serum and saliva of non-smokers, ex-smokers and smokers,” African Health Sciences 18(3), 727–736 (2018).

4. R. B. Silwal, B. Ojha, D. Bajracharya, and G. Silwal, “Correlation of Salivary Thiocyanate levels and Oral Cytological Changes in Smokers,” Journal of College of Medical Sciences-Nepal 16(4), 259–266 (2020).

5. K. Tsuge, M. Kataoka, and Y. Seto, “Cyanide and thiocyanate levels in blood and saliva of healthy adult volunteers,” Journal of Health Science 46(5), 343–350 (2000).

6. K. Guze, H. C. Pawluk, M. Short, H. Zeng, J. Lorch, C. Norris, and S. Sonis, “Pilot study: Raman spectroscopy in differentiating premalignant and malignant oral lesions from normal mucosa and benign lesions in humans,” Head & Neck 37(4), 511–517 (2015).

7. A. Musumeci, D. Gosztola, T. Schiller, N. M. Dimitrijevic, V. Mujica, D. Martin, and T. Rajh, “SERS of semiconducting nanoparticles (TiO2 hybrid composites),” Journal of the American Chemical Society 131(17), 6040–6041 (2009).

8. X. Liu, L. Shi, W. Jiang, J. Zhang, and L. Huang, “Taking full advantage of KMnO4 in simplified Hummers method: A green and one pot process for the fabrication of alpha MnO2 nanorods on graphene oxide,” Chemical Engineering Science 192, 414–421 (2018).

9. X. Zhao-Hui, L. Zhao-Lin, M. Fang-Wei, S. Li-Ping, H. Li-Hua, and Z. Hui, “Hydrothermal Synthesis of alpha-MnO2 Nanorods and Their Electrochemical Performances,” Chinese Journal of Inorganic Chemistry 28(4), 691–697 (2012).

10. H. Luo, Y. Yang, B. Yang, Z. Xu, and D. Wang, “Silver/manganese dioxide nanorod catalyzed hydrogen-borrowing reactions and tert-butyl ester synthesis,” Journal of Chemical Research 45(7-8), 708–715 (2021).

11. Y. Feng, R. Mo, L. Wang, C. Zhou, P. Hong, and C. Li, “Surface enhanced Raman spectroscopy detection of sodium thiocyanate in milk based on the aggregation of Ag nanoparticles,” Sensors 19(6),1363 (2019).

12. A. Nizamuddin, F. Arith, J. Rong, M. Zaimi, A. S. Rahimi, and S. Saat, “Investigation of copper (I) thiocyanate (CuSCN) as a hole transporting layer for perovskite solar cells application,” Journal of Advanced Research in Fluid Mechanics and Thermal Sciences 78(2), 153–159 (2020).

13. Q. Tong, W. Wang, Y. Fan, and L. Dong, “Recent progressive preparations and applications of silver-based SERS substrates,” TrAC Trends in Analytical Chemistry 106, 246–258 (2018).

14. Y. Zhang, R. J. Liu, X. Ma, X. Y. Liu, Y. X. Zhang, and J. Zhang, “Ag nanoparticle decorated MnO 2 flakes as flexible SERS substrates for rhodamine 6G detection,” RSC Advances 8(66), 37750–37756 (2018).

15. T. Jiang, L. Zhang, H. Jin, X. Wang, and J. Zhou, “In situ controlled sputtering deposition of gold nanoparticles on MnO2 nanorods as surface-enhanced Raman scattering substrates for molecular detection,” Dalton Transactions 44(16), 7606–7612 (2015).

16. L. Wu, Z. Wang, S. Zong, and Y. Cui, “Rapid and reproducible analysis of thiocyanate in real human serum and saliva using a droplet SERS-microfluidic chip,” Biosensors and Bioelectronics 62, 13–18 (2014).

17. A. Hussain, H. Pu, and D. W. Sun, “SERS detection of sodium thiocyanate and benzoic acid preservatives in liquid milk using cysteamine functionalized core-shelled nanoparticles,” Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 229, 117994 (2020).

18. Z. Wang, C. Ma, Y. Wu, J. Gu, C. Zhu, L. Li, and G. Chen, “A sensitive method for detecting sodium thiocyanate using AgNPs and MIL-101 (Fe) combined as SERS substrate,” Vibrational Spectroscopy 117, 103311 (2021).

19. F. PulliShery, G. S. Panchmal, and S. SiDDique, “Salivary thiocyanate, uric acid and pH as biomarkers of periodontal disease in tobacco users and non-users-an in-vitro study,” Journal of Clinical and Diagnostic Research 9(7), ZC47–ZC50 (2015).

20. Z. Ma, Y. Zhai, Z. Chen, H. Yang, and F. Wang, “Preparation of QSS@ AuNPs and Solvent Inducing Enhancement Strategy for Raman Determination of Salivary Thiocyanate,” ACS Applied Materials & Interfaces 13(5), 5966–5974 (2021).

21. M. P. Noland, R. J. Kryscio, R. S. Riggs, L. H. Linville, L. J. Perritt, and T. C. Tucker, “Saliva cotinine and thiocyanate: Chemical indicators of smokeless tobacco and cigarette use in adolecents,” Journal of Behavioral Medicine 11, 423–433 (1988).

22. I. M. Colceriu-Șimon, M. Hedeșiu, V. Toma, G. Armencea, A. Moldovan, G. Știufiuc, B. Culic, V. Țărmure, C. Dinu, I. Berindan-Neagoe, and R. I. Știufiuc, “The effects of low-dose irradiation on human saliva: A surface-enhanced raman spectroscopy study,” Diagnostics 9(3), 101 (2019).

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