Efficient Determination of Butylated Hydroxyanisole Using an Electrochemical Sensor Based on Cobalt Oxide Nanoparticles Modified Electrode

Document Type: Research Paper


Department of Chemistry, University of Ilam, Ilam, Iran


A simple and reliable electrochemical sensor based on cobalt oxide nanoparticles modified glassy carbon electrode (GCE/CoOxNPs) for determination of butylated hydroxyanisole is presented here. The nanoparticles were fabricated by electrodepositing method. The modified electrode shows excellent catalytic activity toward butylated hydroxyanisole oxidation in pH 12.0 phosphate buffer solution (PBS). The detection limit (S/N = 3), sensitivity and catalytic rate constant (kcat) of the modified electrode toward butylated hydroxyanisole were 2.9 µM, 5.1 nA μM-1 and 1.1 × 104 M-1 s-1, respectively, at linear concentration rang up to 1350 μM. The capability of the modified electrode for direct butylated hydroxyanisole quantification in real samples is also discussed. This modified electrode shows many advantages such as good catalytic activity, good reproducibility, simple preparation procedure and long-term stability of signal response during butylated hydroxyanisole oxidation. In this report, compared with most cases previously reported, the detection potential of the BHA occurs at a lower potential.


[1] S.J.R. Prabakar,S.S. Narayanan, Surface modification of amine-functionalised graphite for preparation of cobalt hexacyanoferrate (CoHCF)-modified electrode: an amperometric sensor for determination of butylated hydroxyanisole (BHA), Anal. Bioanal. Chem. 386 (2006) 2107-2115.

[2] K.H.G. Freitas, O. Fatibello-Filho, Simultaneous determination of butylated hydroxyanisole (BHA) and butylated hydroxytoluene (BHT) in food samples using a carbon composite electrode modified with Cu3(PO4)2 immobilized in polyester resin, Talanta 81 (2010) 1102-1108.

[3] C. Fuente, J.A. Acuna, M.D. Vazquez, M.L. Tascon, P.S. Batanero, Voltammetric determination of the phenolic antioxidants 3-ter-butyl-4-hydroxyanisole and tert-butylhydroquinone at a polypyrrole electrode modified with a nickel phthalocyanine complex, Talanta 49 (1999) 441-452.

[4] B.D. Page, C.F. Charbonneau, Liquid chromatographic determination of seven antioxidants in dry foods, J Aoac. Int. 72 (1989) 259–265.

[5] S.J.R. Prabakar, S.S. Narayanan, Flow injection analysis of BHA by NiHCF modified electrode, Food Chem. 118 ( 2010) 449-455.

[6] Y.N. Ni; L. Wang, S. Kokot, Voltammetric determination of butylated hydroxyanisole, butylated hydroxytoluene, propyl gallate and Tert-butylhydroquinone by use of chemometric Approaches, Anal. Chim. Acta. 412 (2000) 185-193.

[7] P.Y. Sedeno, J.M. Fingarron, L.M.P. Diez, Determination of tert-butylhydroxyanisole and tert-butylhydroxytoluene by flow injection with amperometric detection, Anal. Chim. Acta, 252 (1991) 153-159.

[8] K.T. Hartman, L.C. Rose, A rapid gas chromatographic method for the determination of BHA and BHT in vegetable oils, J. Am. Oil. Chem. Soc. 47 (l970) 7-10.

[9] M. H. Yang, H.J. Lin, Y.M. Choong, A rapid gas chromatographic method for direct determination of BHA, BHT and TBHQ in edible oils and fats, Food. Res. Int. 35 (2002) 627–633.

[10] C.S. Sactry, K.E. Rao, U.V. Prasad, Spectrophotometric determination of some phenols with sodium metaperiodate and aminophenols, Talanta 29 (1982) 917-920.

[11] P. Christian, M. Liliane, Quantification of synthetic phenolic antioxidants in dry foods by reversed-phase HPLC with photodiode array detection, Food Chem. 77 (2002) 93-100.

[12] M.M. Delgado, I.G. Maza, A.S. Perez, R.C. Martinez, Analysis of synthetic phenolic antioxidants in edible oils by micellar electrokinetic capillary chromatography, Food Chem. 100 (2007) 1722-1727.

[13] T.F. Tormin, D.T. Gimenes, E.M. Richter, R.A.A. Munoz, Fast and direct determination of butylated hydroxyanisole in biodiesel by batch injection analysis with amperometric detection, Talanta 85 (2011) 1274-1278.

[14] P.A. Dimovasilis, M.I. Prodromidis, An Electrochemical Sensor for Trace Uranium Determination Based on 6-O-palmitoyl-L-ascorbic acid-modified Graphite Electrodes. Sens. Actua. B: Chem. 156 (2011) 689-694.

[15] S. Pakapongpan, R. Palangsuntikul, W. Surareungchai, Electrochemical sensors for hemoglobin and myoglobin detection based on methylene blue- multiwalled carbon nanotubes nanohybrid modified glassy carbon electrode, Electrochim. Acta 56 (2011) 6831-6836.

[16] S.A. Wring, J.P. Hart, Chemically modified carbon-based electrodes and their application as electrochemical sensors for the analysis of biologically important compounds, Analyst 117 (1992) 1215-1229.

[17] M. Roushani, M. Shamsipur, H.R. Rajabi, Highly selective detection of dopamine in the presence of ascorbic acid and uric acid using thioglycolic acid capped CdTe quantum dots modified electrode, J. Electroanal. Chem. 712 (2014) 19-24.

[18] M. Roushani, M. Shamsipur, S.M. Pourmortazavi, Amprometric detection of Glycine, l-Serine and l-Alanine using glassy carbon electrode modified by NiO nanoparticles. J. Appl. Electrochem, 12 (2012) 1005-1011.

[19] M. Roushani, M. Sarabaegi, Electrochemical detection of butylated hydroxyanisole based on glassy carbon electrode modified by iridium oxide nanoparticles. J. Electroanal. Chem. 717-718 (2014) 147-152.

[20] A. Salimi, R. Hallaj, B. Kavosi, B. Hagighi, Highly sensitive and selective amperometric sensors for nanomolar detection of iodate and periodate based on glassy carbon electrode modified with iridium oxide nanoparticles. Anal. Chim. Acta 661 (2010) 28–34.

[21] M. Roushani, Z. Abdi, A. Daneshfar, A. Salimi, Hydrogen peroxide sensor based on riboflavin immobilized at the nickel oxide nanoparticle modified glassy carbon electrode, J. Appl. Electrochem. 43 (2013) 1175-1183.

[22] O.A. Petrii, G.A. Tsirlina, Size effects in electrochemistry, Russ. Chem. Rev. 70 (2001) 285–298.

[23] M. Roushani, Z. Abdi, Novel electrochemical sensor based on graphene quantum dots/ riboflavin nanocomposite for the detection of persulfate,Sens. Actua. B: Chem. 201(2014) 503-510.

[24] P.M.S. Monk, S. Ayub, Solid-state properties of thin film electrochromic cobalt–nickel oxide, Solid State Ionics 99 (1997) 115-124.

[25] L.D. Kadam, S.H. Pawar, P.S. Patil, Studies on ionic intercalation properties of cobalt oxide thin films prepared by spray pyrolysis technique, Mater. Chem. Phys. 68 (2001) 280-282.

[26] V. Srinivasan, J.W. Weidner, Capacitance studies of cobalt oxide films formed via electrochemical precipitation, J. Power Sources 108 (2002) 15-20.

[27] Y. Ueda, N. Kikuchi, S. Ikeda, T. Houga, Magnetoresistance and compositional modulation near the layer boundary of Co/Cu multilayers produced by pulse electrodeposition, J. Magn. Mater 198 (1999) 740-742.

[28] I.G. Casella, M.R. Guascito, Electrochemical preparation of a composite gold–cobalt electrode and its electrocatalytic activity in alkaline medium, Electrochim. Acta 45 (1999) 1113–1120.

[29] M. Houshmand, A. Jabbari, H. Heli, M. Hajjizadeh, A.A. Moosavi Movahedi, Electrocatalytic oxidation of aspirin and acetaminophen on a cobalt hydroxide nanoparticles modified glassy carbon electrode, J. Solid State Electrochem. 12 (2008) 1117-1128.

[30] I.G. Casella, Electrodeposition of cobalt oxide films from carbonate solutions containing Co(II)-tartrate complexes, J. Electroanal. Chem. 520 (2002) 119-125.

[31] L.F. Fan, X.Q. Wu, M.D. Guo, Y.T. Gao. Cobalt hydroxide film deposited on glassy carbon electrode for electrocatalytic oxidation of hydroquinone. Electrochim. Acta. 52 (2007) 3654-3659.

[32] A. Salimi, R. Hallaj, S. Soltanian, H. Mamkhezri, Nanomolar detection of hydrogen peroxide on glassy carbon electrode modified with electrodeposited cobalt oxide nanoparticles, Anal. Chim. Acta. 594 (2007) 24-31.

[33] A. Salimi, H. Mamkhezri, R. Hallaj, S. Soltanian. Electrochemical detection of trace amount of arsenic(III) at glassy carbon electrode modified with cobalt oxide nanoparticles, Sens. Actua. B: Chem. 129 (2008) 246-254.

[34] A.P. Brown, F.C. Anson, Cyclic and differential pulse voltammetric behavior of reactants confined to the electrode surface, Anal. Chem. 49 (1977) 1589-1595.

[35] C.P. Andrieux, J.M. Saveant, Heterogeneus (Chemically modified electrodes, Polymer elecreode) VS. Homogeneous catalysis of electrochemical reactions, Electroanal. Chem. 93 (1978) 163-168.

[36] M. Cui, S. Liu, W. Lian, J. Li, W. Xu, J. Huang, A molecularly imprinted electrochemical sensor based on graphene-prussian blue composites modified glassy carbon electrode for the detection of butylated hydroxyanisole in foodstuffs, Analyst 138 (2013) 5949-5955.

[37] D. Jayasri, S.S. Narayanan, Electrocatalytic oxidation and amperometric determination of BHA at graphite-wax composite electrode with silver hexacyanoferrate as electrocatalyst, Sens. Actua. B: Chem. 119 (2006) 135-142.

[38]. D. Jayasri, S.S. Narayanan, Manganese(II) hexacyanoferrate based renewable amperometric sensor for the determination of butylated hydroxyanisole in food products, Food Chem. 101 (2007) 607-614.

[39] S. Kumar, S.S. Narayanan, Mechanically immobilized nickel aquapentacyanoferrate modified electrode as an amperometric sensor for the determination of BHA, Talanta 76 (2008) 54-59.

[40] P.R. Caramit, A.G.F. Andrade, J.B.G. Souza, T.A. Araujo, L.H. Viana, M.A.G. Trindade, V.S. Ferreira, A new voltammetric method for the simultaneous determination of the antioxidants TBHQ and BHA in biodiesel using multi-walled carbon nanotube screen-printed electrodes, Fuel 105 (2013) 306-313.

[41] X. Lin, Y. Ni, Y. S. Kokot, Glassy carbon electrodes modified with gold nanoparticles for the simultaneous determination of three food antioxidants, Anal.Chim. Acta 765 (2013) 54- 62.