Silver nanoparticles with reduced graphene oxide for surface-enhanced vibrational spectroscopy of DNA constituents

  • Siim Heinsalu
  • Olena Fesenko
  • Aleksei Treshchalov
  • Serhii Kovalchuk
  • Andrii Yaremkevych
  • Vladyslav KavelinEmail author
  • Leonid DolgovEmail author
Original Article


Composite of silver nanoparticles with reduced graphene oxide flakes is proposed for surface enhanced vibrational spectroscopy, particularly for detection of adenine and thymine as constituents of deoxyribonucleic acid. Composite was formed by original method implying simultaneous reduction of silver ions and graphene oxide by discharge plasma at the gas–liquid interface. Combination of nanosized silver with reduced graphene oxide provided greater enhancement of Raman light scattering and infrared light absorption in comparison with separately used components. Addition of the composite to water solutions of adenine and thymine allowed detection of these analytes at micromolar concentrations. Composite of nano-silver with reduced graphene oxide can be prospective for surface enhanced spectroscopy as an alternative to the expensive lithographically prepared noble metal substrates.


Surface Enhanced Raman Scattering (SERS) Surface Enhanced InfraRed Absorption (SEIRA) Silver nanoparticles Reduced graphene oxide Adenine Thymine Discharge plasma 



This work was supported by FP7 Marie Curie ILSES project no. 612620 and NATO SPS project NUKR.SFPP984702.

Supplementary material

13204_2018_924_MOESM1_ESM.docm (386 kb)
Supplementary material 1 (DOCM 386 KB)


  1. Avci E, Culha M (2013) Influence of droplet drying configuration on surface enhanced Raman scattering performance. RSC Adv 3:17829–17836. CrossRefGoogle Scholar
  2. Bilal M, Bilal M, Saleem M, Khurram M, Khan S, Ullah R, Ali H, Ahmed M, Shahzada S, Khan E (2017) Raman spectroscopy based investigation of molecular changes associated with an early stage of dengue virus infection. Laser Phys 27(4):045601. CrossRefGoogle Scholar
  3. Butler H, Ashton L, Bird B, Cinque G, Curtis K, Dorney J, Esmonde-White K, Fullwood N, Gardner B, Martin-Hirsch P, Walsh M (2016) Using Raman spectroscopy to characterize biological materials. Nat Protoc 11(4):664–687. CrossRefGoogle Scholar
  4. Cheng F, Yang X, Gao J (2015) Ultrasensitive detection and characterization of molecules with infrared plasmonic metamaterials. Sci Rep UK 5:14327. CrossRefGoogle Scholar
  5. Cialla D, Pollok S, Steinbrücker C, Weber K, Popp J (2014) SERS-based detection of biomolecules. Nanophotonics 3(6):383–411. CrossRefGoogle Scholar
  6. Deegan R, Bakajin O, Dupont T, Huber G, Nagel S, Witten T (1997) Capillary flow as the cause of ring stains from dried liquid drops. Nature 389:827–829CrossRefGoogle Scholar
  7. Dolgov L, Pidhirnyi D, Dovbeshko G, Lebedieva T, Kiisk V, Heinsalu S, Lange S, Jaaniso R, Sildos I (2016) Graphene-enhanced Raman scattering from the adenine molecules. Nanoscale Res Lett 11:197–197. CrossRefGoogle Scholar
  8. Faber C, Attaccalite C, Olevano V, Runge E, Blase X (2011) First-principles GW calculations for DNA and RNA nucleobases. Phys Rev B 83:115123. CrossRefGoogle Scholar
  9. Gelder J, Gussem K, Vandenabeele P, Moens L (2007) Reference database of Raman spectra of biological molecules. J Raman Spectrosc 38(9):1133–1147. CrossRefGoogle Scholar
  10. Genslein C, Hausler P, Kirchner E, Bierl R, Baeumner A, Hirsch T (2017) Detection of small molecules with surface plasmon resonance by synergistic plasmonic effects of nanostructured surfaces and graphene. Proc SPIE. CrossRefGoogle Scholar
  11. Guex L, Sacchi B, Peuvot K, Andersson R, Pourrahimi A, Ström V, Farris S, Olsson R (2017) Experimental review: chemical reduction of graphene oxide (GO) to reduced graphene oxide (rGO) by aqueous chemistry. Nanoscale 9:9562–9571. CrossRefGoogle Scholar
  12. Hope G, Woods R, Munce C (2001) Raman microprobe mineral identification. Miner Eng 14(12):1565–1577. CrossRefGoogle Scholar
  13. Hummers W, Offeman R (1958) Preparation of graphitic oxide. J Am Chem Soc 80:1339–1339CrossRefGoogle Scholar
  14. Ishikawa M, Maruyama Y, Ye J, Futamata M (2002) Single-molecule imaging and spectroscopy of adenine and an analog of adenine using surface-enhanced Raman scattering and fluorescence. J Lumin 98:81–89. CrossRefGoogle Scholar
  15. Jin L, Yue D, Xu Z, Liang G, Zhang Y, Zhang J, Zhang X, Wang Z (2014) Fabrication, mechanical properties, and biocompatibility of reduced graphene oxide reinforced nanofiber mats. RSC Adv 4:35035–35041. CrossRefGoogle Scholar
  16. Ju L, Geng B, Horng J, Girit C, Martin M, Hao Z, Bechtel H, Liang X, Zettl A, Shen Y, Wang F (2011) Graphene plasmonics for tunable terahertz metamaterials. Nat Nanotechnol 6:630–634CrossRefGoogle Scholar
  17. Kruszewski S (1998) Enhancement mechanisms in the SERS phenomenon. Proc SPIE. CrossRefGoogle Scholar
  18. Li M, Huang L, Wang X, Song Z, Zhao W, Wang Y, Liu J (2018) Direct generation of Ag nanoclusters on reduced graphene oxide nanosheets for efficient catalysis, antibacteria and photothermal anticancer applications. J Colloid Interface Sci 529:444–451. CrossRefGoogle Scholar
  19. Liang X, Liang B, Pan Z, Lang X, Zhang Y, Wang G, Yin P, Guo L (2015) Tuning plasmonic and chemical enhancement for SERS detection on graphene-based Au hybrids. Nanoscale 7:20188–20196. CrossRefGoogle Scholar
  20. Ling X, Xie L, Fang Y, Xu H, Zhang H, Kong J, Dresselhaus M, Zhang J, Liu Z (2010) Can graphene be used as a substrate for Raman enhancement? Nano Lett 10:553–561. CrossRefGoogle Scholar
  21. Marcano D, Kosynkin D, Berlin J, Sinitskii A, Sun Z, Slesarev A, Alemany L, Lu W, Tour J (2010) Improved synthesis of graphene oxide. ACS Nano 4(8):4806–4814. CrossRefGoogle Scholar
  22. Mathlouthi M, Seuvre A (1984a) FT-IR and laser-Raman spectra of adenine and adenosine. Carbohyd Res 131(1):1–15. CrossRefGoogle Scholar
  23. Mathlouthi M, Seuvre A (1984b) FT-IR and laser-Raman spectra of thymine and thymidine. Carbohyd Res 134(1):23–38. CrossRefGoogle Scholar
  24. Mohammadi A, Nicholls D, Docoslis A (2018) Improving the surface-enhanced Raman scattering performance of silver nanodendritic substrates with sprayed-on graphene-based coatings. Sensors 18(10):3404. CrossRefGoogle Scholar
  25. Murphy S, Huang L, Kamat P (2013) Reduced graphene oxide–silver nanoparticle composite as an active SERS material. J Phys Chem C 117(9):4740–4747. CrossRefGoogle Scholar
  26. Osawa M (2001) Surface-enhanced infrared absorption. In: Kawata S (ed) Near-field optics and surface plasmon polaritons. Springer, Berlin, pp 163–187 (Topics Appl. Phys. 81)CrossRefGoogle Scholar
  27. Patsha A, Sahoo P, Amirthapandian S, Prasad A, Das A, Tyagi A, Cotta M, Dhara S (2015) Localized charge transfer process and surface band bending in methane sensing by GaN nanowires. J Phys Chem C 119(36):21251–21260. CrossRefGoogle Scholar
  28. Sathe V, Parimaladevi R, Mahalingam U (2019) Graphene boosted silver nanoparticles as surface enhanced Raman spectroscopic sensors and photocatalysts for removal of standard and industrial dye contaminants. Sens Actuators B Chem 281:679–688. CrossRefGoogle Scholar
  29. Scriven L (1988) Physics and applications of DIP coating and spin coating. MRS Proc 121:717–729CrossRefGoogle Scholar
  30. Sharma B, Frontiera R, Henry A, Ringe E, Duyne R (2012) SERS: Materials, applications, and the future. Mater Today 15(1–2):16–25. CrossRefGoogle Scholar
  31. Theophanides T (1978) Infrared and Raman spectroscopy of biological molecules. Springer, DordrechtGoogle Scholar
  32. Treshchalov A, Tsarenko S, Avarmaa T, Saar R, Lõhmus A, Vanetsev A, Sildos I (2016a) He/H2 pulsed-discharge plasma as a tool for synthesis of surfactant-free colloidal silver nanoparticles in water. Plasma Med 6:85–100. CrossRefGoogle Scholar
  33. Treshchalov A, Erikson H, Puust L, Tsarenko S, Saar R, Vanetsev A, Tammeveski K, Sildos I (2016b) Stabilizer-free silver nanoparticles as efficient catalysts for electrochemical reduction of oxygen. J Colloid Interface Sci 491:358–366. CrossRefGoogle Scholar
  34. Xu W, Mao N, Zhang J (2013) Graphene: a platform for surface-enhanced Raman spectroscopy. Small 9(8):1206–1224. CrossRefGoogle Scholar
  35. Yguerabide J, Yguerabide E (1998) Light-scattering submicroscopic particles as highly luminescent analogs and their use as tracer labels in clinical and biological applications. 1. Theory. Anal Biochem 262:137–156CrossRefGoogle Scholar
  36. Zhang D, Xie Y, Mrozek M, Ortiz C, Davisson V, Ben-Amotz D (2003) Raman detection of proteomic analytes. Anal Chem 75:5703–5709. CrossRefGoogle Scholar
  37. Zheng F, Xu W, Jin H, Hao X, Ghiggino K (2015) Charge transfer from poly(3-hexylthiophene) to graphene oxide and reduced graphene oxide. RSC Adv 5(109):89515–89520. CrossRefGoogle Scholar

Copyright information

© King Abdulaziz City for Science and Technology 2018

Authors and Affiliations

  1. 1.Faculty of Science and Engineering, Waseda UniversityTokyoJapan
  2. 2.Institute of PhysicsUniversity of TartuTartuEstonia
  3. 3.Institute of PhysicsNAS of UkraineKievUkraine
  4. 4.Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, School of Chemistry, Sun Yat-Sen UniversityGuangzhouPeople’s Republic of China

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