Microchimica Acta

, 185:504 | Cite as

A needle-like reusable surface-enhanced Raman scattering substrate, and its application to the determination of acetamiprid by combining SERS and thin-layer chromatography

  • Yan Kang
  • Ting Wu
  • Xiaozhen HanEmail author
  • Haixin Gu
  • Xin ZhangEmail author
Original Paper


A micro surface-enhanced Raman scattering (SERS) substrate has been fabricated by electrochemical deposition of dendrite-like gold on carbon fiber needles (Au-CFNs). Scanning electron microscopy and energy dispersive spectroscopy were used to confirm the presence of the gold nanostructure on the CFNs. This substrate has a Raman scattering enhancement factor as high as 3.3 × 10^7 when using rhodamine 6G as the reporter molecule. The high SERS sensitivity is attributed to the massive hotspots on gold bulges that enhance the local surface plasmon resonance. The Au-CFN substrate was reproduced 10 times after electrochemically wiping off the analytes from the needle-like electrode. The substrate has attractive features such as convenient sampling, low sample dosage, and minimal invasion. It was applied, in combination with thin-layer chromatography, for the determination of acetamiprid on vegetables. The result was more accurate because the sample information of both the surface and the bulk can be obtained at the same time after inserting the tip of this needle substrate into the TLC plate. The limit of detection for acetamiprid is 0.05 μg⋅mL-1 and the linear range is 0.1–10 μg⋅mL-1.

Graphical abstract

A reusable micro needle-like SERS substrate was fabricated and applied for pesticide residue analysis. The SERS signal of acetamiprid can be acquired on the tip of this micro needle-like Au-CFN substrate. This substrate can be reused for 10 times.


Acetamiprid Micro substrate Carbon fiber needles Electrochemical deposition Dendrite-like gold 



This work was supported by Science and Technology Commission of Shanghai Municipality (No.17142202600), Fundamental Research Funds for the Central Universities (No. 222201714047), Natural Science Foundation of Shanghai(18ZR1408100)and Scientific research project of MPS (2016JSYJC31, 2016JSYJB34).

Compliance with ethical standards

Yan Kang has received research grants from Science and Technology Commission of Shanghai Municipality. The author(s) declare that they have no competing interests.

Ethical approval

This article does not contain any studies with human participants or animals performed by any of the authors.

Informed consent

Not applicable.

Supplementary material

604_2018_3034_MOESM1_ESM.docx (891 kb)
ESM 1 (DOCX 890 kb)


  1. 1.
    Huang YF, Zhu HP, Liu GK, Wu DY, Ren B, Tian ZQ (2010) When the signal is not from the original molecule to be detected: chemical transformation of para-aminothiophenol on Ag during the SERS measurement. J Am Chem Soc 132(27):9244–9246. CrossRefPubMedGoogle Scholar
  2. 2.
    Kamińska A, Dzięcielewski I, Weyher JL, Waluk J, Gawinkowski S, Sashuk V, Fiałkowski M, Sawicka M, Suski T, Porowski S (2011) Highly reproducible, stable and multiply regenerated surface-enhanced Raman scattering substrate for biomedical applications. J Mater Chem 21(24):8662–8669. CrossRefGoogle Scholar
  3. 3.
    Yang KH, Liu YC, Yu CC (2008) Enhancements in intensity and stability of surface-enhanced Raman scattering on optimally electrochemically roughened silver substrates. J Mater Chem 18(40):4849–4855. CrossRefGoogle Scholar
  4. 4.
    Chu H, Yang H, Huan S, Shen G, Yu R (2006) Orientation of 6-mercaptopurine SAMs at the silver electrode as studied by Raman mapping and in situ SERS. J Phys Chem B 110(11):5490–5497. CrossRefPubMedGoogle Scholar
  5. 5.
    Shorie M, Kumar V, Kaur H, Singh K, Tomer VK, Sabherwal P (2018) Plasmonic DNA hotspots made from tungsten disulfide nanosheets and gold nanoparticles for ultrasensitive aptamer-based SERS detection of myoglobin. Microchim Acta 185(3):158. CrossRefGoogle Scholar
  6. 6.
    Ren X, Cheshari EC, Qi J, Li X (2018) Silver microspheres coated with a molecularly imprinted polymer as a SERS substrate for sensitive detection of bisphenol A. Microchim Acta 185(4):242. CrossRefGoogle Scholar
  7. 7.
    Wang R, Xu Y, Wang R, Wang C, Zhao H, Zheng X, Liao X, Cheng L (2017) A microfluidic chip based on an ITO support modified with Ag-Au nanocomposites for SERS based determination of melamine. Microchim Acta 184(1):279–287. CrossRefGoogle Scholar
  8. 8.
    Luo Z, Chen L, Liang C, Wei Q, Chen Y, Wang J (2017) Porous carbon films decorated with silver nanoparticles as a sensitive SERS substrate, and their application to virus identification. Microchim Acta 184(9):3505–3511. CrossRefGoogle Scholar
  9. 9.
    Pan Y, Guo X, Zhu J, Wang X, Zhang H, Kang Y, Wu T, Du Y (2015) A new SERS substrate based on silver nanoparticle functionalized polymethacrylate monoliths in a capillary, and it application to the trace determination of pesticides. Microchim Acta 182(9):1775–1782. CrossRefGoogle Scholar
  10. 10.
    Li D, Duan H, Wang Y, Zhang Q, Cao H, Deng W, Li D (2017) On-site preconcentration of pesticide residues in a drop of seawater by using electrokinetic trapping, and their determination by surface-enhanced Raman scattering. Microchim Acta 185(1):10–19. CrossRefGoogle Scholar
  11. 11.
    Zhang YR, Xu YZ, Xia Y, Huang W, Liu FA, Yang YC, Li ZL (2011) A novel strategy to assemble colloidal gold nanoparticles at the water–air interface by the vapor of formic acid. J Colloid Interface Sci 359(2):536–541. CrossRefPubMedGoogle Scholar
  12. 12.
    Durmanov NN, Guliev RR, Eremenko AV, Boginskaya IA, Ryzhikov IA, Trifonova EA, Putlyaev EV, Mukhin AN, Kalnov SL, Balandina MV, Tkachuk AP, Gushchin VA, Sarychev AK, Lagarkov AN, Rodionov IA, Gabidullin AR, Kurochkin IN (2018) Non-labeled selective virus detection with novel SERS-active porous silver nanofilms fabricated by electron beam physical vapor deposition. Sensors Actuators B Chem 257:37–47. CrossRefGoogle Scholar
  13. 13.
    Coluccio ML, Das G, Mecarini F, Gentile F, Pujia A, Bava L, Tallerico R, Candeloro P, Liberale C, De Angelis F, Di Fabrizio E (2009) Silver-based surface enhanced Raman scattering (SERS) substrate fabrication using nanolithography and site selective electroless deposition. Microelectron Eng 86(4):1085–1088. CrossRefGoogle Scholar
  14. 14.
    Aldeanueva-Potel P, Faoucher E, Alvarez-Puebla RA, Liz-Marzán LM, Brust M (2009) Recyclable molecular trapping and SERS detection in silver-loaded agarose gels with dynamic hot spots. Anal Chem 81(22):9233–9238. CrossRefPubMedGoogle Scholar
  15. 15.
    Li X, Chen G, Yang L, Jin Z, Liu J (2010) Multifunctional Au-coated TiO2 nanotube arrays as recyclable SERS substrates for multifold organic pollutants detection. Adv Funct Mater 20(17):2815–2824. CrossRefGoogle Scholar
  16. 16.
    Choi JY, Kim K, Shin KS (2010) Surface-enhanced Raman scattering inducible by recyclable Ag-coated magnetic particles. Vib Spectrosc 53(1):117–120. CrossRefGoogle Scholar
  17. 17.
    Mahurin SM, John J, Sepaniak M, Dai S (2011) A re-usable SERS substrate prepared by atomic layer deposition of alumina on a multi-layer gold and silver film. Appl Spectrosc 65(4):417–422. CrossRefPubMedGoogle Scholar
  18. 18.
    Bu Y, Liu K, Hu Y, Kaneti YV, Brioude A, Jiang X, Wang H, Yu A (2017) Bilayer composites consisting of gold nanorods and titanium dioxide as highly sensitive and self-cleaning SERS substrates. Microchim Acta 184(8):2805–2813. CrossRefGoogle Scholar
  19. 19.
    Carrera P, Espinoza-Montero PJ, Fernández L, Romero H, Alvarado J (2017) Electrochemical determination of arsenic in natural waters using carbon fiber ultra-microelectrodes modified with gold nanoparticles. Talanta 166:198–206. CrossRefPubMedGoogle Scholar
  20. 20.
    Huffman ML, Venton BJ (2009) Carbon-fiber microelectrodes for in vivo applications. Analyst 134(1):18–24. CrossRefPubMedGoogle Scholar
  21. 21.
    Sokolović M, Šimpraga B (2006) Survey of trichothecene mycotoxins in grains and animal feed in Croatia by thin layer chromatography. Food Control 17(9):733–740. CrossRefGoogle Scholar
  22. 22.
    Dawan P, Satarpai T, Tuchinda P, Shiowatana J, Siripinyanond A (2017) A simple analytical platform based on thin-layer chromatography coupled with paper-based analytical device for determination of total capsaicinoids in chilli samples. Talanta 162:460–465. CrossRefPubMedGoogle Scholar
  23. 23.
    Chen Y, Li Q, Jiang H, Wang X (2016) Pt modified carbon fiber microelectrode for electrochemically catalytic reduction of hydrogen peroxide and its application in living cell H2O2 detection. J Electroanal Chem 781:233–237. CrossRefGoogle Scholar
  24. 24.
    Ma W, Ying Y-L, Qin L-X, Gu Z, Zhou H, Li D-W, Sutherland TC, Chen H-Y, Long Y-T (2013) Investigating electron-transfer processes using a biomimetic hybrid bilayer membrane system. Nat Protoc 8:439–450. CrossRefPubMedGoogle Scholar
  25. 25.
    Ru ECL, Blackie E, Meyer AM, Etchegoin PG (2007) Surface enhanced Raman scattering enhancement factors: a comprehensive study. J Phys Chem C 111(37):13794–13803. CrossRefGoogle Scholar
  26. 26.
    Orendorff CJ, Gole A, Sau TK, Murphy CJ (2005) Surface-enhanced Raman spectroscopy of self-assembled monolayers: sandwich architecture and nanoparticle shape dependence. Anal Chem 77(10):3261–3266. CrossRefPubMedGoogle Scholar
  27. 27.
    Yin P, You T, Tan E, Li J, Lang X, Jiang L, Guo L (2011) Characterization of tetrahexahedral gold nanocrystals: a combined study by surface-enhanced Raman spectroscopy and computational simulations. J Phys Chem C 115(37):18061–18069. CrossRefGoogle Scholar
  28. 28.
    He P, Liu H, Li Z, Liu Y, Xu X, Li J (2004) Electrochemical deposition of silver in room-temperature ionic liquids and its surface-enhanced Raman scattering effect. Langmuir 20(23):10260–10267. CrossRefPubMedGoogle Scholar
  29. 29.
    Khlebtsov BN, Khanadeev VA, Panfilova EV, Bratashov DN, Khlebtsov NG (2015) Gold nanoisland films as reproducible SERS substrates for highly sensitive detection of fungicides. ACS Appl Mater Interfaces 7(12):6518–6529. CrossRefPubMedGoogle Scholar
  30. 30.
    Santos EB, Sigoli FA, Mazali IO (2013) Surface-enhanced Raman scattering of 4-aminobenzenethiol on silver nanoparticles substrate. Vib Spectrosc 68:246–250. CrossRefGoogle Scholar
  31. 31.
    Que R, Shao M, Zhuo S, Wen C, Wang S, Lee ST (2011) Highly reproducible surface-enhanced Raman scattering on a capillarity-assisted gold nanoparticle assembly. Adv Funct Mater 21(17):3337–3343. CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Austria, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Research Center of Analysis and Test, School of Chemistry & Molecular EngineeringEast China University of Science and TechnologyShanghaiPeople’s Republic of China
  2. 2.College of JewelryShanghai Jian Qiao UniversityShanghaiPeople’s Republic of China
  3. 3.Shanghai Fire Research Institute of MPSShanghaiPeople’s Republic of China
  4. 4.Shanghai Institute Of Planned Parenthood ResearchShanghaiPeople’s Republic of China

Personalised recommendations