Abstract
The illegal use of clenbuterol (CL), as a growth promoter in animal feeding, is banned in the majority of countries across the world, such as the European Union and China. In this study, a rapid and sensitive method for detecting CL in animal-origin food samples based on liquid-liquid extraction and surface-enhanced Raman spectroscopy (SERS) has been developed for the first time. A twice-oxidized graphene oxide/gold nanoparticles composite substrate was innovatively synthesized and used to enhance the characteristic Raman signal of CL at △v = 1474 cm− 1 and 1608 cm− 1, and no more than 10 min of sample cleanup was required before SERS analysis. The optimized hybrid substrate demonstrated good stability over a period of 240 days, which is more stable than previous studies. Quantitation calculation was performed in the concentration range of 1–100 ng g− 1 with a limit of detection (LOD) as low as 1 ng g− 1. Furthermore, the novel detection method was verified for use in the identification of real samples, and the results were consistent with those of liquid chromatography-tandem mass spectrometry (LC-MS/MS). The simplicity and reliability of the proposed method demonstrate its great potential for practical applications in the field of quality control and food safety.
Similar content being viewed by others
References
Bozzolina C, Leporati M, Gani F, Ferrero C, Vincenti M (2018) Development and validation of an UHPLC-MS/MS method for beta (2)-agonists quantification in human urine and application to clinical samples. J Pharm Biomed Anal 150:15–24
Cheng J, Su XO, Han CQ, Wang S, Zhao YP (2016) Highly sensitive detection of melamine using a one-step sample treatment combined with a portable Ag nanostructure array SERS sensor. PLoS One 11:e0154402
Cheng J, Wang S, Zhang S, Wang PL, Xie JC, Han CQ, Su XO (2019a) Rapid and sensitive determination of clenbuterol residues in animal urine by surface-enhanced Raman spectroscopy. Sensors Actuators B Chem 279:7–14
Cheng J, Zhang S, Wang S, Wang PL, Su XO, Xie JC (2019b) Rapid and sensitive detection of acrylamide in fried food using dispersive solid-phase extraction combined with surface-enhanced Raman spectroscopy. Food Chem 276:157–163
Commission Regulation (EU) 1996/22/EC (1996) The prohibition on the use in stock farming of certain substances having a hormonal or thyrostatic action and of β-agonists. Off J Eur Communities 125:3–9
Commission Regulation (EU) 2002/657/EC (2002) The performance of analytical methods and the interpretation results. Off J Eur Communities 221:8–36
Daubert GP, Mabasa VH, Leung VW, Aaron C (2007) Acute clenbuterol overdose resulting in supraventricular tachycardia and atrial fibrillation. J Med Toxicol 3:56–60
Dutta S, Ray C, Sarkar S, Pradhan M, Negishi Y, Pal T (2013) Silver nanoparticle decorated reduced grapheme oxide (rGO) nanosheet: a platform for SERS based low-level detection of uranyl ion. ACS Appl Mater Interfaces 5:8724–8732
Fang F, Qi Y, Lu F, Yang L (2016) Highly sensitive on-site detection of drugs adulterated in botanical dietary supplements using thin layer chromatography combined with dynamic surface enhanced Raman spectroscopy. Talanta 146:351–357
Feng JY, Hu YX, Grant E, Lu XN (2018) Determination of thiabendazole in orange juice using an MISPE-SERS chemosensor. Food Chem 239:816–822
Gonçalves VCD, Santos KTJ, Zuniga NOC, de Lima VV, Padilha MC, Siqueira CYD, Neto FRA (2017) Optimization of a multiresidue and multiclass analysis method for anabolic agents and beta (2)-agonists in bovine urine by GC-MS/MS. Microchem J 133:551–555
Gui RJ, Jin H, Guo HJ, Wang ZH (2018) Recent advances and future prospects in molecularly imprinted polymers-based electrochemical biosensors. Biosens Bioelectron 100:56–70
Guselnikova O, Postnikov P, Elashnikov R, Miliutina E, Svorcik V, Lyutakov O (2019) Metal-organic framework (MOF-5) coated SERS active gold gratings: a platform for the selective detection of organic contaminants in soil. Anal Chim Acta 1068:70–79
Huang Q, Bu T, Zhang WT, Yan LZ, Zhang MY, Yang QF, Huang LJ, Yang BW, Hu N, Suo YR, Wang JL, Zhang DH (2018) An improved clenbuterol detection by immunochromatographic assay with bacteria@Au composite as signal amplifier. Food Chem 262:48–55
Hou H, Wang P, Zhang J, Li CP, Jin YD (2015) Graphene oxide-supported Ag nanoplates as LSPR tunable and reproducible substrates for SERS applications with optimized sensitivity. ACS Appl Mater Interfaces 7:18038–18045
Izquierdo II, Sanche SZ, Garcia JVR (2010) Adsorption of beta-adrenergic agonists used in sport doping on metal nanoparticles: a detection study based on surface-enhanced Raman scattering. Langmuir 26:14663–14670
Jiang Y, Wang J, Malfatti L, Carboni D, Senes N, Innocenzi P (2018) Highly durable graphene-mediated surface enhanced Raman scattering (G-SERE) nanocomposites for molecular detection. Appl Surf Sci 450:451–460
Jin XC, Fang GZ, Pan MF, Yang YK, Bai XY, Wang S (2018) A molecularly imprinted electrochemiluminescence sensor based on upconversion nanoparticles enhanced by electrodeposited rGO for selective and ultrasensitive detection of clenbuterol. Biosens Bioelectron 102:357–364
Karamolegou F, Dasenaki BV, Georgakilas V, Thomaidis N (2018) Multi-residue determination of 7 beta-agonists in liver and meat using gas chromatography-mass spectrometry. Food Anal Methods 11:2925–2942
Lamberti A, Virga A, Angelini A, Ricci A, Descrovi E, Cocuzza M, Giorgis F (2015) Metal-elastomer nanostructures for tunable SERS and easy microfluidic integration. RSC Adv 5:4404–4410
Li B, Shi Y, Cui J, Liu Z, Zhang X, Zhan J (2016) Au-coated ZnO nanorods on stainless steel fiber for self-cleaning solid phase microextraction-surface enhanced Raman spectroscopy. Anal Chim Acta 923:66–73
Liang J, Liu H, Huang C, Yao C, Fu Q, Li X, Cao D, Luo Z, Tang Y (2015) Aggregated silver nanoparticles based surface-enhanced Raman scattering enzyme-linked immunosorbent assay for ultrasensitive detection of protein biomarkers and small molecules. Anal Chem 87:5790–5796
Ling X, Moura LG, Pimenta MA, Zhang J (2012) Charge transfer mechanism in graphene-enhanced Raman scattering. J Phys Chem C 116:25112–25118
Liu XX, Lu Q, Chen SR, Wang F, Hou JJ, Xu ZL (2018) Selection and identification of novel aptamers specific for clenbuterol based on ssDNA library immobilized SELEX and gold nanoparticles biosensor. Molecules 23:2337
Lv CZ, Xun Y, Cao Z, Xie JL, Li D, Liu G, Yu L, Feng ZM, Yin YL, Tan SZ (2017) Sensitive determination of toxic clenbuterol in pig meat and pig liver based on a carbon nanopolymer composite. Food Anal Methods 10:2252–2261
Ma LY, Nilghaz A, Choi JR, Liu XQ, Lu XN (2018) Rapid detection of clenbuterol in milk using microfluidic paper-based ELISA. Food Chem 246:437–441
Ma YM, Liu HL, Mao M, Meng J, Yang LB, Liu JH (2016) Surface-enhanced Raman spectroscopy on liquid interfacial nanoparticle arrays for multiplex detecting drugs in urine. Anal Chem 88:8145–8151
Medellin-Martinez MF, Luna-Zavala I, Martinez-Delgade M, Perez-Urizar JT, Ramirez-Telles JA, Patino-Rodriguez O (2018) Sensitive assay of Clenbuterol residues in beef by ultra-high performance liquid chromatography coupled with mass spectrometry (UPLC-MS/MS) and solid-phase extraction. Food Anal Methods 11:2561–2568
Ministry of Agriculture of the People’s Republic of China (2008) Determination of β-receptor agonists in animal urine liquid chromatography-tandem mass spectrometry. Regulation No 1063–3
Ministry of Agriculture of the People’s Republic of China (2010) List of banned animal feed and drinking water substances. Bulletin No 1519
National Standards of the People’s Republic of China (2008) Determination of beta-agonists residues in foodstuff of animal origin- liquid chromatography with tandem-mass spectrometric method. GB/T 22286
Panneerselvam R, Liu GK, Wang YH, Liu JY, Ding SY, Li JF, Wu DY, Tian ZQ (2018) Surface-enhanced Raman spectroscopy: bottlenecks and future directions. Chem Commun 54:10–25
Peng T, Wang JY, Zhao SJ, Xie SL, Yao K, Zheng PM, Wang SH, Ke YB, Jiang HY (2018) A fluorometric clenbuterol immunoassay based on the use of organic/inorganic hybrid nanoflowers modified with gold nanoclusters and artificial antigen. Microchim Acta 185:366
Qu XL, Lin H, Du SY, Sui JX, Zhang XL, Cao LM (2016) Development of a Nano-gold capillary immunochromatographic assay for rapid and semi-quantitative detection of clenbuterol residues. Food Anal Methods 9:2531–2540
Sun K, Huang Q, Meng GW, Lu YL (2016) Highly sensitive selective surface enhanced raman spectroscopy label detection of 3,3′,4,4′-tetrachlorobiphenyl using DNA aptamer-modified Ag-nanorod arrays. ACS Appl Mater Interfaces 8:5723–5728
Thatai S, Khurana P, Prasad S, Soni SK, Kumar D (2016) Trace colorimetric detection of Pb2þ using plasmonic gold nanoparticles and silica-gold nanocomposites. Microchem J 124:104–110
Wang ZZ, Jing J, Ren YG, Guo YF, Tao NY, Zhou QW, Zhang HL, Ma YF, Wang YH (2019) Preparation and application of selenium nanoparticles in a lateral flow immunoassay for clenbuterol detection. Mater Lett 234:212–215
Xiao X, Wang YH, Tan W, Liu HJ, Duan YY, Zhang XB, Zhang DE, Jiang YX, Wang J, Gong JY, Ma JJ, Yang T, Tong ZW (2018) Simple synthesis of multilayer-shaped CeO2 nanomaterial and its electrochemical detection of clenbuterol. Electroanalysis 30:2744–2749
Xie Y, Chang HF, Zhao K, Yang H, Mei LY, Xu SM, Deng AP (2015) A novel immunochromatographic assay (ICA) based on surface-enhanced Raman scattering for the sensitive and quantitative determination of clenbuterol. Anal Methods 7:513–520
Yamamoto YS, Itoh T (2016) Why and how do the shapes of surface-enhanced Raman scattering spectra change? Recent progress from mechanistic studies. J Raman Spectrosc 47:78–88
Zaffino C, Bedini GD, Mazzola G, Guglielmi V, Bruni S (2016) Online coupling of high-performance liquid chromatography with surface-enhanced Raman spectroscopy for the identification of historical dyes. J Raman Spectrosc 47:607–615
Zhang CY, Hao R, Zhao B, Fu YZ, Zhang HJ, Moeendarbari S, Pickering CS, Hao YW, Liu YQ (2017) Graphene oxide-wrapped flower-like sliver particles for surface-enhanced Raman spectroscopy and their applications in polychlorinated biphenyls detection. Appl Surf Sci 400:49–56
Zhao AX, Tang XJ, Zhang ZH, Liu JH (2016) Optimizing Savitzky-Golay parameters and its smoothing pretreatment for FTIR gas spectra. Spectrosc Spectr Anal 36:1340–1344
Zhao JH, Yuan HC, Peng YJ, Hong Q, Liu MH (2017) Detection of ractopamine and clenbuterol hydrochloride residues in pork using surface enhanced Raman spectroscopy. J Appl Spectrosc 84:76–81
Zhao YD, Liu X, Lei DY, Chai Y (2014) Effects of surface roughness of Ag thin films on surface-enhanced Raman spectroscopy of graphene: spatial nonlocality and physisorption strain. Nanoscale 6:1311–1317
Zheng TT, Gao ZG, Luo Y, Liu XM, Zhao WJ, Lin BC (2016) Manual-slide-engaged paper chip for parallel SERS-immunoassay measurement of clenbuterol from swine hair. Electrophoresis 37:418–424
Zhou YZ, Cheng XN, Du D, Yang J, Zhao N, Ma SB, Zhong T, Lin YH (2014) Graphene-silver nanohybrids for ultrasensitive surface enhanced Raman spectroscopy: size dependence of silver nanoparticles. J Mater Chem C 2:6850–6858
Zhu GC, Hu YJ, Gao J, Zhong L (2011) Highly sensitive detection of clenbuterol using competitive surface-enhanced Raman scattering immunoassay. Anal Chim Acta 697:61–66
Funding
The project was supported by a special fund for innovation from the Chinese Academy of Agricultural Sciences (The innovation team of testing and evaluation for feed quality & safety).
Author information
Authors and Affiliations
Corresponding authors
Ethics declarations
Conflict of Interest
The authors declare that they have no conflict of interest.
Ethical Approval
This article does not contain any studies with human participants or animals performed by any of the authors.
Informed Consent
Not applicable.
Additional information
Publisher’s Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
ESM 1
(PDF 409 kb)
Rights and permissions
About this article
Cite this article
Cheng, J., Fan, M., Wang, P. et al. The Twice-Oxidized Graphene Oxide/Gold Nanoparticles Composite SERS Substrate for Sensitive Detection of Clenbuterol Residues in Animal-Origin Food Samples. Food Anal. Methods 13, 902–910 (2020). https://doi.org/10.1007/s12161-020-01709-3
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s12161-020-01709-3