Skip to main content
SpringerLink
Log in

Surfactant-Free Facile Synthesis of Ag/rGO Nanohybrid for SERS-Based Detection of Melamine

  • RESEARCH
  • Published:
Plasmonics Aims and scope Submit manuscript

Abstract

Surfactant-free silver nanoparticle-loaded reduced graphene oxide (Ag/rGO) nanohybrids have the potential for fabricating efficient SERS-based sensors. Using surfactants in the synthesis of Ag/rGO nanohybrid often passivates the SERS activity and produces interference in the intrinsic Raman signal of the analytes. And also, the chemical-reducing agents used to synthesize Ag/rGO nanohybrid are toxic and not eco-friendly. Therefore, in this work, we have synthesized a stable Ag/rGO nanohybrid without the aid of a surfactant and toxic reducing agent. The Ag/rGO nanohybrid SERS substrate is tested for the detection of melamine in the range of 1 × 10−3 to 1 × 10−8 M in H2O. The characteristic Raman peak intensity was found to vary linearly with respect to melamine concertation with a correlation coefficient of 0.94 and the enhancement factor is 8.4 × 106. SERS analysis on milk extract could detect 1 × 10−6 M melamine adulteration, one order better than the allowable limit of 2.0 × 10−5 M.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

Data Availability

All data generated in this study appear in the submitted article.

References

  1. Xiao G, Li L, Yan A, He X (2019) Direct detection of melamine in infant formula milk powder solution based on SERS effect of silver film over nanospheres. Spectrochim Acta A Mol 22:117269

  2. Kobun R, Siddiquee S (2015) A review of recent advances in melamine detection techniques. J Food Compos Anal 43:25–38

    Article  Google Scholar 

  3. Brown CA, Jeong KS, Poppenga RH, Puschner B, Miller DM, Ellis AE, Kang KI, Sum S, Cistola AM, Brown SA (2007) Outbreaks of renal failure associated with melamine and cyanuric acid in dogs and cats in 2004 and 2007. J Vet Diagn 19:525–531

    Article  Google Scholar 

  4. Limin L, Chin WS (2021) Rapid and sensitive SERS detection of melamine in milk using Ag nanocube array substrate coupled with multivariate analysis. Food Chem 357:129717

  5. Dalal R, Goldfarb D (2011) Melamine-related kidney stones and renal toxicity. Nat Rev Nephrol 7:267–274

    Article  CAS  PubMed  Google Scholar 

  6. Filazi A, Sireli UT, Ekici H, Can HY, Karagoz A (2012) Determination of melamine in milk and dairy products by high performance liquid chromatography. J Dairy Sci 95:602–608

    Article  CAS  PubMed  Google Scholar 

  7. Aurélien D, Miriam GC, Thierry D, Pascal M (2009) Screening and confirmatory methods for the determination of melamine in cow’s milk and milk-based powdered infant formula: validation and proficiency-tests of ELISA, HPLC-UV, GC-MS and LC-MS/MS. J Agric Food Chem 57:7186–7193

    Google Scholar 

  8. Lutter P, Savoy-Perroud MC, Campos-Gimenez E, Meyer L, Goldmann T, Bertholet MC, Mottier P, Desmarchelier A, Monard F, Perrin C, Robert F, Delatour T (2011) Screening and confirmatory methods for the determination of melamine in cow’s milk and milk-based powdered infant formula: validation and proficiency-tests of ELISA, HPLC-UV, GC-MS and LC-MS/MS. Food Control 22:903–913

    Article  CAS  Google Scholar 

  9. Chang K, Wang S, Zhang H, Guo Q, Hu X, Lin Z, Sun H, Jiang M, Hu J (2017) Colorimetric detection of melamine in milk by using gold nanoparticles-based LSPR via optical fibers. PLoS ONE 12:e0177131

    Article  PubMed  PubMed Central  Google Scholar 

  10. Xin JY, Zhang LX, Chen DD, Lin K, Fan HC, Wang Y, Xia CG (2015) Colorimetric detection of melamine based on methanobactin-mediated synthesis of gold nanoparticles. Food chem 174:473–479

    Article  CAS  PubMed  Google Scholar 

  11. Song J, Wu F, Wan Y, Ma L (2015) Colorimetric detection of melamine in pretreated milk using silver nanoparticles functionalized with sulfanilic acid. Food Control 50:356–361

    Article  CAS  Google Scholar 

  12. Xu ML, Gao Y, Han XX, Zhao B (2022) Innovative application of SERS in food quality and safety: a brief review of recent trends. Foods 11(14):2097

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  13. Cong S, Liu X, Jiang Y, Zhang W, Zhao Z (2020) Surface enhanced Raman scattering revealed by interfacial charge-transfer transitions. The Innovation 1(3)

  14. Langer J, Jimenez de Aberasturi D, Aizpurua J, Alvarez-Puebla RA, Auguié B, Baumberg JJ, Bazan GC, Bell SE, Boisen A, Brolo AG, Choo J (2020) Present and future of surface-enhanced Raman scattering. ACS Nano 14:28–117

    Article  CAS  PubMed  Google Scholar 

  15. Lee HK, Lee YH, Koh CS, Phan-Quang GC, Han X, Lay CL, Sim HY, Kao YC, An Q, Ling XY (2019) Designing surface-enhanced Raman scattering (SERS) platforms beyond hotspot engineering: emerging opportunities in analyte manipulations and hybrid materials. Chem Soc Rev 48:731–756

    Article  CAS  PubMed  Google Scholar 

  16. Gokulakrishnan J, Alex KV, Sekhar KC, Koppole K (2022) Highly sensitive, cost-effective, and flexible SERS substrate based on green synthesized GO/rGO for pesticide detection. ChemistrySelect 7(20):e202200348

  17. Bhavya S, Renee RF, Anne-Isabelle H, Emilie R, Richard P (2012) Van Duyne SERS: Materials, applications, and the future. Mater Today 15:16–25

    Article  Google Scholar 

  18. Lai H, Li G, Zhang Z (2023) SnS2/AuNPs surface-enhanced Raman scattering sensor for rapid and selective quantification of methimazole in serum and meat samples. Sens Actuators B: Chem 380

  19. Hernandez S, Garcia L, Perez-Estebanez M, Cheuquepan W, Heras A, Colina A (2022) Multiamperometric-SERS detection of melamine on gold screen-printed electrodes. J Electroanal Chem 918:116478 (2022) Multiamperometric-SERS detection of melamine on gold screen-printed electrodes. J Electroanal Chem 918:116478

  20. Huy BT, Pham QT, An NT, Conte E, Lee YI (2017) Development of a simple method for sensing melamine by SERS effect of Ag particles. J Lumin 188:436–440

  21. Zhuang H, Zhu W, Yao Z, Li M, Zhao Y (2016) SERS-based sensing technique for trace melamine detection – a new method exploring. Talanta 153:186–190

  22. Huang WC, Cheng KF, Shyu JY (2022) Flexible SERS substrate of silver nanoparticles on cotton swabs for rapid in situ detection of melamine. Nanoscale Adv 4:1164–1172

  23. Kumar D, Tiwari R, Patel RK, Adhikary P, Krishnamoorthi S (2021) One-pot synthesis of electroconducting graphene coated silver nanoparticles from silver acetylide. J Nanopart Res 23:162

  24. Kaushik V, Kagdada HL, Singh DK, Pathak S (2022) Enhancement of SERS effect in Graphene-Silver hybrids. Appl Surf Sci 574:151724

  25. Zhao H, Fu H, Zhao T, Wang L, Tan T (2012) Fabrication of small-sized silver NPs/graphene sheets for high-quality surface-enhanced Raman scattering. J Colloid Interface Sci 375:30–34

  26. Lai H, Xu F, Zhang Y, Wang L (2018) Recent progress on graphene-based substrates for surface-enhanced Raman scattering applications. J Mater Chem B 6(24):4008–4028

    Article  CAS  PubMed  Google Scholar 

  27. Wang Z, Liu J, Wang J, Ma Z, Kong D, Jiang S, Luo D, Liu YJ (2022) Graphene oxide-coated metal-insulator-metal SERS substrates for trace melamine detection. Nanomaterials 12(7):1202

  28. Lu L, Xu L, Zhang Y, Jiang T (2022) Multiplexed surface-enhanced Raman scattering detection of melamine and dicyandiamide in dairy food enabled by three-dimensional polystyrene@silver@graphene oxide hybrid substrate. Appl Surf Sci 603:154419

  29. Tian J, Liu S, Zhang Y, Li H, Wang L, Luo Y, Asiri AM, Al-Youbi AO, Sun X (2012) Environmentally friendly, one-pot synthesis of Ag nanoparticle-decorated reduced graphene oxide composites and their application to photocurrent generation. Inorg Chem 51:4742–4746

  30. Chen Z, Lu S, Zhang Z, Huang X, Zhao H, Wei J, Li F, Yuan K, Su L, Xiong Y (2022) Green photoreduction synthesis of dispersible gold nanoparticles and their direct in situ assembling in multidimensional substrates for SERS detection. Mikrochim Acta 189(8):275

  31. Benzait Z, Chen P, Trabzon L (2021) Trabzon enhanced synthesis method of graphene oxide. Nanoscale Adv 3:223–230

  32. Salahaldin A, Muhannad A (2020) Investigating the structural, optical and antibacterial properties of Go, Go: Ag, GO: ZnO thin layers and Go: ZnO/ GO: Ag bilayers synthesized by spray pyrolysis Method Iran. J Mater Sci Eng 17 (4)

  33. Ahmad MA, Aslam S, Mustafa F, Arshad U (2021) Synergistic antibacterial activity of surfactant free Ag–GO nanocomposites. Sci Rep 11:196

  34. Li M, Yan L, Si J, Li X, Li J, Hou X (2020) Enhancement mechanism of the saturable absorption effect in reduced graphene oxide decorated with silver nanoparticles. Opt Mater Express 10:884–890

  35. Cottancin E, Celep G, Lermé J, Pellarin M, Huntzinger J, Vialle J, Broyer M (2006) Optical properties of noble metal clusters as a function of the size: comparison between experiments and a semi-quantal theory. Theor Chem Acc 116:514–523

  36. Link S, El-Sayed MA (1999) Spectral properties and relaxation dynamics of surface plasmon electronic oscillations in gold and silver nanodots and nanorods. J Phys Chem B 10:8410–8426

  37. Liu Y, Zhang H, Geng Y, Xu S, Xu W, Yu J, Deng W, Yu B, Wang L (2020) long-range surface plasmon resonance configuration for enhancing SERS with an adjustable refractive index sample buffer to maintain the symmetry condition. ACS Omega 5:32951–32958

  38. Bhargava R (1953) Khan S (2018) Structural, optical and dielectric properties of graphene oxide. AIP Conf Proc 1:030011

  39. Ikram M, Raza A, Imran M, Ul-Hamid A, Shahbaz A, Ali S (2020) Hydrothermal synthesis of silver decorated reduced graphene oxide (rGO) nanoflakes with effective photocatalytic activity for wastewater treatment Nanoscale Res. Lett 15:95

  40. Maharubin S, Zhang X, Zhu F, Zhang HC, Zhang G, Zhang Y (2016) Synthesis and applications of semiconducting graphene. J Nanomater 6375962

  41. Li P, Wang X, Zhang X, Zhang L, Yang X, Zhao B (2019) Investigation of the charge-transfer between Ga-doped ZnO nanoparticles and molecules using surface-enhanced Raman scattering: doping induced band-gap shrinkage. Anal Chem 7:144

  42.  Hidayah NM, Liu WW, Lai CW, Noriman NZ, Khe CS, Hashim U, Lee HC (2017) Comparison on graphite, graphene oxide and reduced graphene oxide: Synthesis and characterization. AIP Conf Proc 1892(1):150002

  43. Kumar A, Sadanandhan AM, Jain SL (2019) Silver doped reduced graphene oxide as a promising plasmonic photocatalyst for oxidative coupling of benzylamines under visible light irradiation. New J Chem 43:9116–9122

  44. Guerrero-Contreras J, Caballero-Briones F (2015) Graphene oxide powders with different oxidation degree, prepared by synthesis variations of the Hummers method. Mater Chem Phys 153:1–12

  45. Xiaodong L (2018) Preparation of graphene oxide and its application as substrates for SERS. J Chem 8050524

  46. Lombardi J, Birke R (2008) A unified approach to surface-enhanced Raman spectroscopy. J Phys Chem C 112:5605–5617

  47.  Marrani AG, Motta A, Palmieri V, Perini G, Papi M, Dalchiele EA, Schrebler R, Zanoni R (2020) A compared experimental and theoretical study of the mechanism of graphene oxide mild reduction by ascorbic acid and N-acetyl cysteine for biomedical application. Mater Adv 1:2745–2754

  48. Chis V, Mile G, Stiufiuc R, Leopold N, Oltean M (2009) Vibrational and electronic structure of PTCDI and melamine–PTCDI complexes. J Mol Struct 47:924–926

  49. Han X, Zhao B (2020) Surface-enhanced Raman scattering (SERS) and applications, in molecular and laser spectroscopy, 2nd volume Elsevier, United Kingdom. 349–386

  50. Xiu L, Xiao-Juan Z, Ting-Ting Y, Guang-Sheng W (2016) Peng-Gang Yi, Lin G Controlled assembly of one-dimensional MoO3@Au hybrid nanostructures as SERS substrates for sensitive melamine detection. Cryst Eng Comm 18(40):7805–7813

  51. Lipsa S, Bigyan RJ, Aruna KB, Priyaranjan M (2022) Preparation and characterization of silver nanoparticles/graphene oxide hybrid nanofiller reinforced-polyaniline, plastics, rubber and composites. Plast Rubber Compos 51:72–84

  52. Dong Y, Wang Q, Wan L, You X, Chi Y (2016) Carbon based dot capped silver nanoparticles for efficient surface-enhanced Raman scattering. J Mater Chem C 4(31):7472–7477

  53. Mekonnen ML, Su WN, Chen CH, Hwang BJ (2017) Ag@SiO2 nanocube loaded miniaturized filter paper as a hybrid flexible plasmonic SERS substrate for trace melamine detection. Anal Methods 9:6823–6829

  54. Zhang C, You T, Yang N, Gao Y, Jiang L, Yin P (2019) Hydrophobic paper-based SERS platform for direct-droplet quantitative determination of melamine. Food Chem 287:363–368

Download references

Acknowledgements

The author P.A. Manojkumar is thankful to Dr. R. Divakar, Dir. MSG, Dr. S.K. Dhara, Head-SSSD, and Dr. S. Tripurasundari, Head-SDS for their encouragement and support.

Author information

Authors and Affiliations

  1. Department of Science and Humanities, Indian Institute of Information Technology Tiruchirappalli, Tiruchirappalli, 620012, Tamil Nadu, India

    Gokulakrishnan J & Kamakshi Koppole

  2. Surface and Nanoscience Division, Materials Science Group, Indira Gandhi Centre for Atomic Research (IGCAR), Kalpakkam, 603102, India

    P. A. Manojkumar

Authors
  1. Gokulakrishnan J
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. P. A. Manojkumar
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Kamakshi Koppole
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

The author Gokulakrisnan J contributed to the methodology, conceptualized and formulated the studies, carried out the experiments, collected data, and analyzed and wrote the original draft. The author P.A. Manojkumar provided resources and technical discussions and reviewed the manuscript. The author Kamakshi Koppole supervised the studies and reviewed the manuscript. All authors have given approval to the final version of the manuscript.

Corresponding author

Correspondence to Kamakshi Koppole.

Ethics declarations

Ethics Approval

The authors assure that this paper is the authors’ own original work, which has not been previously published elsewhere. The paper is not currently being considered for publication elsewhere. The paper reflects the authors’ own research and analysis in a truthful and complete manner.

Consent to Participate

All authors agreed to participate in this research.

Consent for Publication

All authors of this paper agree to publish.

Conflict of Interest

The authors declare no competing interests.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

J, G., Manojkumar, P.A. & Koppole, K. Surfactant-Free Facile Synthesis of Ag/rGO Nanohybrid for SERS-Based Detection of Melamine. Plasmonics 19, 471–480 (2024). https://doi.org/10.1007/s11468-023-01999-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11468-023-01999-3

Keywords

Search

Navigation