Skip to main content
SpringerLink
Log in

Highly sensitive and selective determination of melamine in milk using glassy carbon electrode modified with molecularly imprinted copolymer

  • Published:
Food Analytical Methods Aims and scope Submit manuscript

Abstract

A novel electrochemical sensor was constructed for highly sensitive and selective determination of melamine by depositing a molecularly imprinted copolymer film, prepared by electrocopolymerization of gallic acid and o-phenylenediamine from aqueous electrolyte solution, onto glassy carbon electrode surface. The morphologic feature of the modified electrode was characterized via cyclic voltammetry, electrochemical impedance spectrometry, and scanning electron microscopy. The interactions between the molecularly imprinted copolymer and melamine cause the decrease in the peak currents of hexacyanoferrate, which could be used for electrochemical sensing of melamine. In this study, square wave voltammetry was selected as transducing mechanism. Several important parameters controlling the performance of the molecularly imprinted polymer (MIP) electrode were investigated and optimized. In the optimal conditions, the sensor response was sensitive to melamine from 5.0 to 100.0 nmol L−1 with good selectivity. The limit of detection based on a signal to noise ratio of 3 was low up to 1.4 nmol L−1. The method was applied successfully to determine melamine in milk products with satisfactory precision (2.11~3.38 % of relative standard deviation (RSD)) and acceptable recoveries (96.6~106.4 %), demonstrating a promising feature for applying the MIP sensor to trace detection of melamine in milk and other related products.

ᅟ

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

Similar content being viewed by others

References

  • Aghaei A, Milani Hosseini MR, Najafi M (2010) A novel capacitive biosensor for cholesterol assay that uses an electropolymerized molecularly imprinted polymer. Electrochim Acta 55(5):1503–1508

    Article  CAS  Google Scholar 

  • Araujo WRD, Paixão TRLC (2014) Use of copper electrode for melamine quantification in milk. Electrochim Acta 117:379–384

    Article  Google Scholar 

  • Cao Q, Zhao H, Zeng LX, Wang J, Wang R, Qiu XH, He YJ (2009) Electrochemical determination of melamine using oligonucleotides modified gold electrodes. Talanta 80:484–488

    Article  CAS  Google Scholar 

  • Chen D, Deng J, Liang J, Xie J, Huang KH, Hu CH (2013) Core-shell magnetic nanoparticles with surface-imprinted polymer coating as a new adsorbent for solid phase extraction of metronidazole. Anal Methods 5:722–728

    Article  CAS  Google Scholar 

  • Cheng Y, Dong YY, Wu JH, Yang XR, Bai H, Zheng HY, Ren DM, Zou YD, Li M (2010) Screening melamine adulterant in milk powder with laser Raman spectrometry. J Food Compos Anal 23(2):199–202

    Article  CAS  Google Scholar 

  • Cheng WJ, Liu ZJ, Wang Y (2013) Preparation and application of surface molecularly imprinted silica gel for selective extraction of melamine from milk samples. Talanta 116:396–402

    Article  CAS  Google Scholar 

  • Dai HC, Shi Y, Wang YL, Sun YJ, Hu JT, Ni PG, Li Z (2014) A carbon dot based biosensor for melamine detection by fluorescence resonance energy transfer. Sens Actuators B 202:201–208

    Article  CAS  Google Scholar 

  • 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(2):602–608

    Article  CAS  Google Scholar 

  • Gómez-Caballero A, Unceta N, Aranzazu Goicolea M, Barrio RJ (2008) Evaluation of the selective detection of 4,6-dinitro-o-cresol by a molecularly imprinted polymer based microsensor electrosynthesized in a semiorganic media. Sens Actuators B 130:713–722

    Article  Google Scholar 

  • Gómez-Caballero A, Ugarte A, Sánchez-Ortega A, Unceta N, Goicolea MA, Barrio RJ (2010) Molecularly imprinted poly[tetra(o-aminophenyl)porphyrin] as a stable and selective coating for the development of voltammetric sensors. J Electroanal Chem 638(2):246–253

    Article  Google Scholar 

  • Hao XJ, Zhou XH, Zhang Y, Liu LH, Long F, Song L, Shi HC (2014) Melamine detection in dairy products by using a reusable evanescent wave fiber-optic biosensor. Sens Actuators B 204:682–687

    Article  CAS  Google Scholar 

  • Hrichi H, Louhaichi MR, Monser L, Adhoum N, Gliclazide (2014) Voltammetric sensor based on electropolymerized molecularly imprinted polypyrrole film onto glassy carbon electrode. Sens Actuators B 204:42–49

    Article  CAS  Google Scholar 

  • Kim B, Perkins LB, Bushway RJ, Nesbit S, Fan T, Sheridan R, Greene V (2008) Determination of melamine in pet food by enzyme immunoassay, high-performance liquid chromatography with diode array detection, and ultra-performance liquid chromatography with tandem mass spectrometry. J AOAC Int 91(2):408–413

    CAS  Google Scholar 

  • Klampfl CW, Andersen L, Haunschmidt M, Himmelsbach M, Buchberger W (2009) Analysis of melamine in milk powder by CZE using UV detection and hyphenation with ESI quadrupole/TOF MS detection. Electrophoresis 30(10):1743–1746

    Article  CAS  Google Scholar 

  • Li JP, Zhao J, Wei XP (2009) A sensitive and selective sensor for dopamine determination based on a molecularly imprinted electropolymer of o-aminophenol. Sens Actuators B 140:663–669

    Article  CAS  Google Scholar 

  • Li C, Li YY, Liang B, Li N, Li ZZ (2013) A simple and sensitive method for the determination of melamine in milk by first derivative UV spectrophotometry coupled with the H-point standard addition method. Anal Methods 5(20):5760–5766

    Article  CAS  Google Scholar 

  • Liang RN, Zhang RM, Qin W (2009) Potentiometric sensor based on molecularly imprinted polymer for determination of melamine in milk. Sens Actuators B 144(2):544–550

    Article  Google Scholar 

  • Lin M, He L, Awika J, Yang L, Ledoux DR, Li H, Mustapha A (2008) Detection of melamine in gluten, chicken feed, and processed foods using surface enhanced Raman spectroscopy and HPLC. J Food Sci 73(8):T129–T134

    Article  CAS  Google Scholar 

  • Liu Y, Song QJ, Wang L (2009) Development and characterization of an amperometric sensor for triclosan detection based on electropolymerized molecularly imprinted polymer. Microchem J 91:222–226

    Article  CAS  Google Scholar 

  • Liu YT, Deng J, An L, Liang J, Chen F, Wang H (2011a) Spectrophotometric determination of melamine in milk by rank annihilation factor analysis based on pH gradual change-UV spectral data. Food Chem 126(2):745–750

    Article  CAS  Google Scholar 

  • Liu YT, Deng J, Xiao XL, Ding L, Yuan YL, Li H, Li XT, Yan XN, Wang LL (2011b) Electrochemical sensor based on a poly(para-aminobenzoic acid) film modified glassy carbon electrode for the determination of melamine in milk. Electrochim Acta 56:4595–4602

    Article  CAS  Google Scholar 

  • Maouche N, Guergouri M, Gam-Derouich S, Jouini M, Nessark B, Chehimi MM (2012) Molecularly imprinted polypyrrole films: some key parameters for electrochemical picomolar detection of dopamine. J Electroanal Chem 685:21–27

    Article  CAS  Google Scholar 

  • Matsui J, Higashi M, Takeuchi T (2000) Molecularly imprinted polymer as 9-ethyladenine receptor having a porphyrin-based recognition center. J Am Chem Soc 122(21):5218–5219

    Article  CAS  Google Scholar 

  • Mazzotta E, Malitesta C (2010) Electrochemical detection of the toxic organohalide 2,4-DB using a Co-porphyrin based electrosynthesized molecularly imprinted polymer. Sens Actuators B 148:186–194

    Article  CAS  Google Scholar 

  • Mazzotta E, Picca RA, Malitesta C, Piletsky SA, Piletska EV (2008) Development of a sensor prepared by entrapment of MIP particles in electrosynthesised polymer films for electrochemical detection of ephedrine. Biosens Bioelectron 23(7):1152–1156

    Article  CAS  Google Scholar 

  • Muñiz-Valencia R, Ceballos-Magaña S, Rosales-Martinez D, Gonzalo-Lumbreras R, Santos-Montes A, Cubedo-Fernandez-Trapiella A, Izquierdo-Hornillos R (2008) Method development and validation for melamine and its derivatives in rice concentrates by liquid chromatography. Application to animal feed samples. Anal Bioanal Chem 392:523–531

    Article  Google Scholar 

  • Nong YF, Ma XG, Fan SF, Yu YM (2014) A fast and low-cost method for determination of melamine in soil and sediment using high performance liquid chromatography. Anal Methods 6:4124–4129

    Article  CAS  Google Scholar 

  • Özcan L, Şahin Y (2007) Determination of paracetamol based on electropolymerized-molecularly imprinted polypyrrole modified pencil graphite electrode. Sens Actuators B 127:362–369

    Article  Google Scholar 

  • Ozkorucuklu SP, Sahin Y, Alsancak G (2008) Voltammetric behaviour of sulfamethoxazole on electropolymerized-molecularly imprinted overoxidized polypyrrole. Sensors 8:8463–8478

    Article  CAS  Google Scholar 

  • Panasyuk TL, Mirsky VM, Piletsky SA, Wolfbeis OS (1999) Electropolymerized molecularly imprinted polymers as receptor layers in capacitive chemical sensors. Anal Chem 71:4609–4613

    Article  CAS  Google Scholar 

  • Pardieu E, Cheap H, Vedrine C, Lazerges M, Lattach Y, Garnier F, Remita S, Pernelle C (2009) Molecularly imprinted conducting polymer based electrochemical sensor for detection of atrazine. Anal Chim Acta 649(2):236–245

    Article  CAS  Google Scholar 

  • Peng H, Liang CD, Zhou AH, Zhang YY, Xie QJ, Yao SZ (2000) Development of a new atropine sulfate bulk acoustic wave sensor based on a molecularly imprinted electrosynthesized copolymer of aniline with o-phenylenediamine. Anal Chim Acta 423(2):221–228

    Article  CAS  Google Scholar 

  • Pietrzyk A, Kutner W, Chitta R, Zandler ME, D’Souza F, Sannicolò F, Mussini PR (2009) Melamine acoustic chemosensor based on molecularly imprinted polymer film. Anal Chem 81:10061–10070

    Article  CAS  Google Scholar 

  • Prasad BB, Tiwari MP, Madhuri R, Sharma PS (2010) Enatioselective quantitative separation of d- and l-thyroxine by molecularly imprinted micro-solid phase extraction silver fiber coupled with complementary molecularly imprinted polymer-sensor. J Chromatogr A 1217:4255–4266

    Article  CAS  Google Scholar 

  • Radi AE, El-Naggar AE, Nassef HM (2014) Determination of coccidiostat clopidol on an electropolymerized-molecularly imprinted polypyrrole polymer modified screen printed carbon electrode. Anal Methods 6(19):7967–7972

    Article  CAS  Google Scholar 

  • Rima J, Abourida M, Xu T, Cho IK, Kyriacos S (2009) New spectrophotometric method for the quantitative determination of melamine using Mannich reaction. J Food Compos Anal 22(7):689–693

    Article  CAS  Google Scholar 

  • Song W, Chen Y, Xu J, Tian DB (2010) A selective voltammetric detection for dopamine using poly (gallic acid) film modified electrode. Chin Chem Lett 21:349–352

    Article  CAS  Google Scholar 

  • Sun FX, Ma W, Xu LG, Zhu YY, Liu LQ, Peng CF, Wang LB, Kuang H, Xu CL (2010) Analytical methods and recent developments in the detection of melamine. TrAC Trends Anal Chem 29:1239–1249

    Article  CAS  Google Scholar 

  • Syritski V, Reut J, Menaker A, Gyurcsányi RE, Öpik A (2008) Electrosynthesized molecularly imprinted polypyrrole films for enantioselective recognition of l-aspartic acid. Electrochim Acta 53:2729–2736

    Article  CAS  Google Scholar 

  • Ulyanova YV, Blackwell AE, Minteer SD (2006) Poly(methylene green) employed as molecularly imprinted polymer matrix for electrochemical sensing. Analyst 131:257–261

    Article  CAS  Google Scholar 

  • Wang K, Guan XW, Chai SG, Zou QC, Zhang XH, Zhang JZ (2015) A novel, molecularly imprinted polymer sensor made using an oligomeric methyl silsesquioxane-TiO2 composite sol on a glassy carbon electrode for the detection of procainamide hydrochloride. Biosens Bioelectron 64:94–101

    Article  CAS  Google Scholar 

  • Wu YT, Huang CM, Lin CC, Ho WA, Lin LC, Chiu TF, Tarng DC, Lin CH, Tsai TH (2009) Oral bioavailability, urinary excretion and organ distribution of melamine in Sprague–Dawley rats by high-performance liquid chromatography with tandem mass spectrometry. J Agric Food Chem 58(1):108–111

    Article  Google Scholar 

  • Yan N, Zhou L, Zhu ZF, Chen XG (2009) Determination of melamine in dairy products, fish feed, and fish by capillary zone electrophoresis with diode array detection. J Agric Food Chem 57(3):807–811

    Article  CAS  Google Scholar 

  • Yan XN, Deng J, Xu JS, Li H, Wang LL, Chen D, Xie J (2012) A novel electrochemical sensor for isocarbophos based on a glassy carbon electrode modified with electropolymerized molecularly imprinted terpolymer. Sens Actuators B 171–172:1087–1094

    Article  Google Scholar 

  • Yang HH, Zhou WH, Guo XC, Chen FR, Zhao HQ, Lin LM, Wang XR (2009a) Molecularly imprinted polymer as SPE sorbent for selective extraction of melamine in dairy products. Talanta 80:821–825

    Article  CAS  Google Scholar 

  • Yang SP, Ding JH, Zheng J, Hu B, Li JQ, Chen HW, Zhou ZQ, Qiao XL (2009b) Detection of melamine in milk products by surface desorption atmospheric pressure chemical ionization mass spectrometry. Anal Chem 81:2426–2436

    Article  CAS  Google Scholar 

  • Yu JH, Zhang CC, Dai P, Ge SG (2009) Highly selective molecular recognition and high throughput detection of melamine based on molecularly imprinted sol–gel film. Anal Chim Acta 651:209–214

    Article  CAS  Google Scholar 

  • Zhan PP, Gong WJ, Zhao YG (2014) Use of core–shell nanoring amino-functionalized superparamagnetic molecularly imprinted polymer for matrix solid phase dispersion extraction and preconcentration of ultratrace levels of BPA from water samples. Anal Methods 6:5546–5553

    Article  CAS  Google Scholar 

  • Zhang J, Wang YQ, Lv RH, Xu L (2010) Electrochemical tolazoline sensor based on gold nanoparticles and imprinted poly-o-aminothiophenol film. Electrochim Acta 55:4039–4044

    Article  CAS  Google Scholar 

  • Zhou LM, Huang JS, Yang L, Li LB, You TY (2014) Enhanced electrochemiluminescence based on Ru(bpy)32 + −doped silica nanoparticles and graphene composite for analysis of melamine in milk. Anal Chim Acta 824(8):57–63

    Article  CAS  Google Scholar 

  • Zhu XL, Wang SH, Liu Q, Xu Q, Xu SX, Chen HL (2009) Determination of residues of cyromazine and its metabolite, melamine, in animal-derived food by gas chromatography–mass spectrometry with derivatization. J Agric Food Chem 57(23):11075–11080

    Article  CAS  Google Scholar 

  • Zou HY, Zhang WL, Feng YY, Liang B (2014) Simultaneous determination of melamine and dicyandiamide in milk by UV spectroscopy coupled with chemometrics. Anal Methods 6:5865–5871

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors acknowledge the financial support of the Hunan Provincial Innovation Foundation for Postgraduate, China (project no. CX2010B378) and the Hunan Technology Department Foundation, China (no. 2013FJ3028).

Conflict of interest

Jian Deng declares that he has no conflict of interest. Saiqin Ju declares that she has no conflict of interest. Yating Liu declares that she has no conflict of interest. Ni Xiao declares that she has no conflict of interest. Jin Xie declares that he has no conflict of interest. Haiqing Zhao declares that she has no conflict of interest, and this article does not contain any studies with human or animal subjects.

Author information

Authors and Affiliations

  1. College of Chemistry and Chemical Engineering, University of South China, Hengyang, Hunan, 421001, China

    Jian Deng, Saiqin Ju, Ni Xiao, Jin Xie & Haiqing Zhao

  2. Jiangxi Jingde PVMTech Co. Ltd., Jingdezhen, Jiangxi, 333000, China

    Yating Liu

Authors
  1. Jian Deng
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Saiqin Ju
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yating Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Ni Xiao
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Jin Xie
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Haiqing Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Jian Deng.

Electronic supplementary material

Below is the link to the electronic supplementary material.

ESM 1

(DOC 389 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Deng, J., Ju, S., Liu, Y. et al. Highly sensitive and selective determination of melamine in milk using glassy carbon electrode modified with molecularly imprinted copolymer. Food Anal. Methods 8, 2437–2446 (2015). https://doi.org/10.1007/s12161-015-0134-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12161-015-0134-6

Keywords

Search

Navigation