Abstract
Illegally use of enrofloxacin in chicken has raised serious concerns due to its negative effects on public health. In this study, surface-enhanced Raman spectroscopy (SERS) using amino-modified glycidyl methacrylate-ethylene dimethacrylate (GMA-EDMA) powdered porous material was developed and validated to detect enrofloxacin in chicken muscles. By this method, enrofloxacin in chicken muscles was successfully detected at a concentration of 0.01 mg kg−1, which was lower than the legal maximum residue limit. And the unique “fingerprint-like” spectral patterns of enrofloxacin obtained from SERS spectra could be used for identification and characterization. Compared with high-performance liquid chromatography, the assay of six samples with SERS was rapid in less than 40 min, and the detection was highly sensitive. The results demonstrate that SERS using GMA-EDMA powdered porous material can be potentially employed as a screening tool for rapid detection of residual drugs in a large amount of food samples.
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References
Bell SEJ, Sirimuthu NMS (2008) Quantitative surface-enhanced Raman spectroscopy. Chem Soc Rev 37:1012–1024
Brown SA (1996) Fluoroquinolones in animal health. J Vet Pharmacol Ther 19:1–14
Chen J, Xu F, Jiang H, Hou Y, Rao Q, Guo P, Ding S (2009) A novel quantum dot-based fluoroimmunoassay method for detection of enrofloxacin residue in chicken muscle tissue. Food Chem 113:1197–1201
Cheng Y, Dong Y (2011) Screening melamine contaminant in eggs with portable surface-enhanced Raman spectroscopy based on gold nanosubstrate. Food Control 22:685–689
Commission Decision of 12 August 2002 implementing Council Directive 96/23/EC concerning the performance of analytical methods and the interpretation of results, Official Journal of the European Communities L221/8/17.8.2002
Cox LA Jr (2006) Enrofloxacin in poultry and human health. Emerg Infect Dis 12:872–873
Fabrega A, Sanchez-Cespedes J, Soto S, Vila J (2008) Quinolone resistance in the food chain. Int J Antimicrob Agents 31:307–315
He L, Kim NJ, Li H, Hu Z, Lin M (2008) Use of a fractal-like gold nanostructure in surface-enhanced Raman spectroscopy for detection of selected food contaminants. J Agric Food Chem 56:9843–9847
He L, Lin M, Li H, Kim NJ (2010) Surface-enhanced Raman spectroscopy coupled with dendritic silver nanosubstrate for detection of restricted antibiotics. J Raman Spectrosc 41:739–744
Huang Z, Meng G, Huang Q, Yang Y, Zhu C, Tang C (2010) Improved SERS performance from Au nanopillar arrays by abridging the pillar tip spacing by Ag sputtering. Adv Mater 22:4136–4139
Kim K, Lee JW, Shin KS (2013) Cyanide SERS as a platform for detection of volatile organic compounds and hazardous transition metal ions. Analyst 138:2988–2994
Kneipp J, Kneipp H, Kneipp K (2008) SERS—a single-molecule and nanoscale tool for bioanalytics. Chem Soc Rev 37:1052–1060
Lee P, Meisel D (1982) Adsorption and surface-enhanced Raman of dyes on silver and gold sols. J Phys Chem 86:3391–3395
Li D, Qu L, Zhai W, Xue J, Fossey JS, Long Y (2011) Facile on-site detection of substituted aromatic pollutants in water using thin layer chromatography combined with surface-enhanced Raman spectroscopy. Environ Sci Technol 45:4046–4052
Li JF, Huang YF, Ding Y, Yang ZL, Li SB, Zhou XS, Fan FR, Zhang W, Zhou ZY, de Wu Y, Ren B, Wang ZL, Tian ZQ (2010a) Shell-isolated nanoparticle-enhanced Raman spectroscopy. Nature 464:392–395
Li QQ, Du YP, Xu Y, Wang X, Ma SQ, Geng JP, Cao P, Sui T (2013) Rapid and sensitive detection of pesticides by surface-enhanced Raman spectroscopy technique based on glycidyl methacrylate–ethylene dimethacrylate (GMA–EDMA) porous material. Chin Chem Lett 24:332–334
Li Q, Du Y, Tang H, Wang X, Chen G, Iqbal J, Wang W, Zhang W (2012) Ultra sensitive surface-enhanced Raman scattering detection based on monolithic column as a new type substrate. J Raman Spectrosc 43:1392–1396
Li Y, Song C, Zhang L, Zhang W, Fu H (2010b) Fabrication and evaluation of chiral monolithic column modified by β-cyclodextrin derivatives. Talanta 80:1378–1384
Lin M (2010) The application of surface-enhanced Raman spectroscopy to identify and quantify chemical adulterants or contaminants in foods. Handbook of vibrational spectroscopy, vol. 2. John Wiley & Sons, New York, pp 649–662
Lombardi JR, Birke RL (2009) A unified view of surface-enhanced Raman scattering. Acc Chem Res 42:734–742
Moskovits M (2005) Surface-enhanced Raman spectroscopy: a brief retrospective. J Raman Spectrosc 36:485–496
Sajan D, Sockalingum GD, Manfait M, Hubert Joe I, Jayakumar VS (2008) NIR-FT Raman, FT-IR and surface-enhanced Raman scattering spectra, with theoretical simulations on chloramphenicol. J Raman Spectrosc 39:1772–1783
Skoulika SG, Georgiou CA (2001) Rapid quantitative determination of ciprofloxacin in pharmaceuticals by use of solid-state FT-Raman spectroscopy. Appl Spectrosc 55:1259–1265
Stoilova NA, Surleva AR, Stoev G (2012) Simultaneous determination of nine quinolones in food by liquid chromatography with fluorescence detection. Food Anal Methods 6:803–813
Stubbings G, Bigwood T (2009) The development and validation of a multiclass liquid chromatography tandem mass spectrometry (LC-MS/MS) procedure for the determination of veterinary drug residues in animal tissue using a QuEChERS (QUick, Easy, CHeap, Effective, Rugged and Safe) approach. Anal Chim Acta 637:68–78
Svec F, Frechet JMJ (1996) New designs of macroporous polymers and supports: from separation to biocatalysis. Science 273:205–211
Svec F, Frechet JMJ (1992) Continuous rods of macroporous polymer as high-performance liquid chromatography separation media. Anal Chem 64:820–822
Tang H, Fang D, Li Q, Cao P, Geng J, Sui T, Wang X, Iqbal J, Du Y (2012a) Determination of tricyclazole content in paddy rice by surface enhanced Raman spectroscopy. J Food Sci 77:T105–T109
Tang YY, Lu HF, Lin HY, Shin YC, Hwang DF (2012b) Development of a quantitative multi-class method for 18 antibiotics in chicken, pig, and fish muscle using UPLC-MS/MS. Food Anal Methods 5:1459–1468
Wang Q, He L, Labuza TP, Ismail B (2013) Structural characterisation of partially glycosylated whey protein as influenced by pH and heat using surface-enhanced Raman spectroscopy. Food Chem 139:313–319
Wei WY, White IM (2012) A simple filter-based approach to surface enhanced Raman spectroscopy for trace chemical detection. Analyst 137:1168–1173
Wu JE, Chang C, Ding WP, He DP (2008) Determination of florfenicol amine residues in animal edible tissues by an indirect competitive ELISA. J Agric Food Chem 56:8261–8267
Xue C, Li Z, Mirkin CA (2005) Large-scale assembly of single-crystal silver nanoprism monolayers. Small 1:513–516
Zhai F, Huang Y, Li C, Wang X, Lai K (2011) Rapid determination of ractopamine in swine urine using surface-enhanced Raman spectroscopy. J Agric Food Chem 59:10023–10027
Zhai F, Huang Y, Wang X, Lai K (2012) Surface-enhanced Raman spectroscopy for rapid determination of ơ-agonists in swine urine. Chin J Anal Chem 40:718–723
Zhang Y, Huang Y, Zhai F, Du R, Liu Y, Lai K (2012) Analyses of enrofloxacin, furazolidone and malachite green in fish products with surface-enhanced Raman spectroscopy. Food Chem 135:845–850
Zhao S, Jiang H, Li X, Mi T, Li C, Shen J (2007) Simultaneous determination of trace levels of 10 quinolones in swine, chicken, and shrimp muscle tissues using HPLC with programmable fluorescence detection. J Agric Food Chem 55:3829–3834
Acknowledgments
The authors gratefully acknowledge the financial support for this project from National Science Foundation of China (grant no: 21205041).
Conflict of interest
Ying Xu declares that she has no conflict of interest. Yiping Du declares that he has no conflict of interest. Qingqing Li declares that she has no conflict of interest. Xuan Wang declares that he has no conflict of interest. Yingcheng Pan declares that he has no conflict of interest. Han Zhang declares that he has no conflict of interest. Ting Wu declares that she has no conflict of interest. Huilian Hu declares that she has no conflict of interest. In this article, all institutional and national guidelines for the care and use of laboratory animals were followed.
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Xu, Y., Du, Y., Li, Q. et al. Ultrasensitive Detection of Enrofloxacin in Chicken Muscles by Surface-Enhanced Raman Spectroscopy Using Amino-Modified Glycidyl Methacrylate-Ethylene Dimethacrylate (GMA-EDMA) Powdered Porous Material. Food Anal. Methods 7, 1219–1228 (2014). https://doi.org/10.1007/s12161-013-9736-z
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DOI: https://doi.org/10.1007/s12161-013-9736-z