Preparation and characterization magnetic polypyrrole composite microspheres decorated with copper(II) as a sensing platform for electrochemical detection of Carbamazepine

Document Type : Research article


1 .Nanochemistry Research Laboratory, Department of Chemistry, University of Birjand, Birjand, Iran.

2 Nanochemistry Research Laboratory, Department of Chemistry, University of Birjand, Birjand, Iran.

3 Pharmaceutical Sciences Research Center, Department of Medicinal Chemistry, Faculty of Pharmacy, Kermanshah University of Medical Sciences, Kermanshah, Iran.


With a facile solvothermal technique, Ssynthesis and application of Fe3O4@PPy–CuIIcomposite microspheres in the carbon ionic liquid matrix have been reported as highly sensitive sensors for voltammetric determination of Carbamazepine (CBZ). The morphology, crystal phase and structure of synthesized The nanocomposite structure was confirmed by routine methods such as transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Fourier translation infrared spectroscopy (FT-IR), thermal gravimetric analysis (TGA), and inductively coupled plasma atomic emission spectroscopy (ICP-AES). Under the optimized conditions, differential pulse voltammetric (DPV) peak current was proportional to the CBZ concentration in the range of 0.05 to 25 μM with the detection limit (S/N=3) of 32 nM.
The storage stability of the modified electrode was also investigated which showes that the current responses remain about 95.2% of their initial values, indicating the appreciable storage stability of this sensor.
The proposed electrode displayed excellent repeatability and long-term stability and it was satisfactorily used for determination of CBZ in real samples (urine, and serum samples) with high recovery.

Graphical Abstract

Preparation and characterization magnetic polypyrrole composite microspheres decorated with copper(II) as a sensing platform for electrochemical detection of Carbamazepine


[1] A.K. Birnbaum, J.M. Conway, N.A. Hardie, T.E. Lackner, S.E. Bowers, I.E. Leppik, Carbamazepine dose–concentration relationship in elderly nursing home residents, Epilepsy research, 77 (2007) 31-35.
[2] Y. Zhang, S.-U. Geißen, C. Gal, Carbamazepine anddiclofenac: removal in wastewater treatment plants and occurrence in water bodies, Chemosphere, 73 (2008) 1151-1161.
[3] R. Kelmann, G. Kuminek, H. Teixeira, L. Koester, Determination of carbamazepine in parenteral nanoemulsions: development and validation of an HPLC method, Chromatographia, 66 (2007) 427-430.
[4] M. Behbahani, F. Najafi, S. Bagheri, M.K. Bojdi, M. Salarian, A. Bagheri, Application of surfactant assisted dispersive liquid–liquid microextraction as an efficient sample treatment techniquefor preconcentration and trace detection of zonisamide and carbamazepine in urine and plasma samples, Journal of Chromatography A, 1308 (2013) 25-31.
[5] J.C. Durán-Alvarez, E. Becerril-Bravo, V.S. Castro, B. Jiménez, R. Gibson, The analysis of a group ofacidic pharmaceuticals, carbamazepine, and potential endocrine disrupting compounds in wastewater irrigated soils by gas chromatography–mass spectrometry, Talanta, 78 (2009) 1159-1166.
[6] E. Marziali, M.A. Raggi, N. Komarova, E. Kenndler, Octakis‐6‐sulfato‐γ‐cyclodextrin as additive for capillary electrokinetic chromatography of dibenzoazepines: Carbamazepine, oxcarbamazepine and their metabolites, Electrophoresis, 23 (2002) 3020-3026.
[7] J. Maggs, M. Pirmohamed, N. Kitteringham, B. Park, Characterization of the metabolites of carbamazepine in patient urine by liquid chromatography/mass spectrometry, Drug Metabolism and Disposition, 25 (1997) 275-280.
[8] S.H. Lee, L. Ming, J.K. Suh, Determination of carbamazepine by chemiluminescence detection using chemically prepared tris (2, 2′-bipyridine) ruthenium (III) as oxidant, Analytical sciences, 19 (2003) 903-906.
[9]  Z. Rezaei, B. Hemmateenejad, S. Khabnadideh, M. Gorgin, Simultaneous spectrophotometric determination of carbamazepine and phenytoin in serum by PLS regression and comparison with HPLC, Talanta, 65 (2005) 21-28.
[10]  A. Fatahi, R. Malakooti, M. Shahlaei, Electrocatalytic oxidation and determination of dexamethasone at an Fe 3 O 4/PANI–Cu II microsphere modified carbon ionic liquid electrode, RSC Advances, 7 (2017) 11322-11330.
[11] M.B. Gholivand, M. Shahlaei, A. Pourhossein, New Zn (II)-Selective Potentiometric Sensor Based on 3-Hydroxy-2-Naphthoic Hydrazide, Sensor Letters, 7 (2009) 119-125.
[12] M. Shahlaei, M.B. Gholivand, A. Pourhossein, Simultaneous Determination of Tyrosine and Histidine by Differential Pulse Cathodic Stripping Voltammetry Using H‐point Standard Addition Method in Tap and Seawater, Electroanalysis, 21 (2009) 2499-2502.
[13] M. Shahlaei, M.B. Gholivand, A. Pourhossein, Application of adsorptive stripping voltammetry for determination of uranium in the presence of 3-hydroxy-2-naphthoic hydrazide, Analytical Letters, 42 (2009) 3085-3095.
[14] R.N. Goyal, V.K. Gupta, M. Oyama, N. Bachheti, Differential pulse voltammetric determination of paracetamol at nanogold modified indium tin oxide electrode, Electrochemistry communications, 7 (2005) 803-807.
[15] L. Cui, S. Ai, K. Shang, X. Meng, C. Wang, Electrochemical determination of NADH using a glassy carbon electrode modifiedwith Fe3O4 nanoparticles and poly-2, 6-pyridinedicarboxylic acid, and its application to the determination of antioxidant capacity, Microchimica Acta, 174 (2011) 31-39.
[16] S. Tian, J. Liu, T. Zhu, W. Knoll, Polyaniline/gold nanoparticle multilayer films: assembly, properties, and biological applications, Chemistry of Materials, 16 (2004) 4103-4108.
[17] P. Xu, X. Han, C. Wang, H. Zhao, J. Wang, X. Wang, B. Zhang, Synthesis of electromagnetic functionalized barium ferrite nanoparticles embedded in polypyrrole, The Journal of Physical Chemistry B, 112 (2008) 2775-2781.
[18] Y. Li, R. Yi, A. Yan, L. Deng, K. Zhou, X. Liu, Facile synthesis and properties of ZnFe 2 O 4 and ZnFe 2 O 4/polypyrrole core-shell nanoparticles, Solid State Sciences, 11 (2009) 1319-1324.
[19] A. Ramanavičius, A. Ramanavičienė, A. Malinauskas, Electrochemical sensors based on conducting polymer—polypyrrole, Electrochimica acta, 51 (2006) 6025-6037.
[20] X. Li, G. He, Y. Han, Q. Xue, X. Wu, S. Yang, Magnetic titania-silica composite–Polypyrrole core–shell spheres and their high sensitivity toward hydrogen peroxide as electrochemical sensor, Journal of colloid and interface science, 387 (2012) 39-46.
[21] L. Özcan, Y. Şahin, H. Türk, Non-enzymatic glucose biosensor based on overoxidized polypyrrole nanofiber electrode modified with cobalt (II) phthalocyanine tetrasulfonate, Biosensors and Bioelectronics, 24 (2008) 512-517.
[22] F. Meng, W. Shi, Y. Sun, X. Zhu, G. Wu, C. Ruan, X. Liu, D. Ge, Nonenzymatic biosensor based on Cu x O nanoparticles deposited on polypyrrole nanowires for improving detectionrange, Biosensors and Bioelectronics, 42 (2013) 141-147.
[23] T. Zheng, X. Lu, X. Bian, C. Zhang, Y. Xue, X. Jia, C. Wang, Fabrication of ternary CNT/PPy/K x MnO 2 composite nanowires for electrocatalytic applications, Talanta, 90 (2012) 51-56.
[24] A. Nan, R. Turcu, I. Bratu, C. Leostean, O. Chauvet, E. Gautron, J. Liebscher, Novel magnetic core-shell Fe3O4 polypyrrole nanoparticles functionalized by peptides or albumin, Arkivoc, 2010 (2010) 185-198.
[25]  Z. Bai, L. Yang, Y. Guo, Z. Zheng, C. Hu, P. Xu, High-efficiency palladium catalysts supported on ppy-modified C 60 for formic acid oxidation, Chemical Communications, 47 (2011) 1752-1754.
[26] M.A. Correa‐Duarte, N. Sobal, L.M. Liz‐Marzán, M. Giersig, Linear Assemblies of Silica‐Coated Gold Nanoparticles Using Carbon Nanotubes as Templates, Advanced Materials, 16 (2004) 2179-2184.
[27] N. Lavanya, S. Radhakrishnan, C. Sekar, M. Navaneethan, Y. Hayakawa, Fabrication of Cr doped SnO 2 nanoparticles based biosensor for the selective determination of riboflavin in pharmaceuticals, Analyst, 138 (2013) 2061-2067.
[28] H. Heli, M. Hajjizadeh, A. Jabbari, A. Moosavi-Movahedi, Copper nanoparticles-modified carbon paste transducer as a biosensor for determination of acetylcholine, Biosensors and Bioelectronics, 24 (2009) 2328-2333.
[29] L. Pan, Y. Chen, F. Wang, Synthesis of nanostructured M/Fe 3 O 4 (M= Ag, Cu) composites using hexamethylentetramine and their electrocatalytic properties, Materials Chemistry and Physics, 134 (2012) 177-182.
[30] M. Opallo, A. Lesniewski, A review on electrodes modified with ionic liquids, Journal of Electroanalytical Chemistry, 656 (2011) 2-16.
[31] B. Liu, W. Zhang, F. Yang, H. Feng, X. Yang, Facile method for synthesis of Fe3O4@ polymer microspheres and their application as magnetic support for loading metal nanoparticles, The Journal of Physical Chemistry C, 115 (2011) 15875-15884.
[32] D.E. Park, H.S. Chae, H.J. Choi, A. Maity, Magnetite–polypyrrole core–shellstructured microspheres and their dual stimuli-response under electric and magnetic fields, Journal of Materials Chemistry C, 3 (2015) 3150-3158.
[33] E. Brancewicz, E. Grądzka, A.Z. Wilczewska, K. Winkler, Polymeric p–n Nanojunctions: Formation and Electrochemical Properties of C60‐Pd@ Polypyrrole Core–Shell Nanoparticles, ChemElectroChem, 2 (2015) 253-262.
[34] J. Stejskal, M. Trchová, I.A. Ananieva, J. Janča, J. Prokeš, S. Fedorova, I. Sapurina, Poly (aniline-co-pyrrole): powders, films, and colloids. Thermophoretic mobility of colloidal particles, Synthetic metals, 146 (2004) 29-36.
[35] X. Yang, L. Li, Polypyrrole nanofibers synthesized via reactive template approach and their NH 3 gas sensitivity, Synthetic metals, 160 (2010) 1365-1367.
[36] J. Meng, J. Bu, C. Deng, X. Zhang, Preparation of polypyrrole-coated magnetic particles for micro solid-phase extraction of phthalates in water by gas chromatography–mass spectrometry analysis, Journal of Chromatography A, 1218 (2011) 1585-1591.
[37]Y. Sun, L. Wang, D. Yu, N. Tang, J. Wu, Zinc/magnesium–sodium/lithium heterobimetallic triphenolates: Synthesis, characterization, and application as catalysts in the ring-opening polymerization of l-lactide and CO 2/epoxide coupling, Journal of Molecular CatalysisA: Chemical, 393 (2014) 175-181.
[38] U.G. Singh, R.T. Williams, K.R. Hallam, G.C. Allen, Exploring the distribution of copper–Schiff base complex covalently anchored onto the surface of mesoporous MCM 41 silica, Journal of Solid State Chemistry, 178 (2005) 3405-3413.
[39] N. Yang, Q. Wan, J. Yu, Adsorptive voltammetry of Hg (II) ions at a glassy carbon electrode coated with electropolymerized methyl-red film, Sensors and Actuators B: Chemical, 110 (2005) 246-251.
[40] L. Molero, M. Faundez, M.A. del Valle, R. del Río, F. Armijo, Electrochemistry of methimazole on fluorine-doped tin oxide electrodes and its square-wave voltammetric determination in pharmaceutical formulations, Electrochimica acta, 88 (2013) 871-876.
[41] Y. Wu, X. Ji, S. Hu, Studies on electrochemical oxidation of azithromycin and its interaction with bovine serum albumin, Bioelectrochemistry, 64 (2004) 91-97.
[42] B. Unnikrishnan, V. Mani, S.-M. Chen, Highly sensitive amperometric sensor for carbamazepine determination based on electrochemically reduced graphene oxide–single-walled carbon nanotube composite film, Sensors and Actuators B: Chemical, 173 (2012) 274-280.
[43] A.J. Bard, L.R. Faulkner, Fundamentals and applications, Electrochemical Methods, 2 (2001).
[44] S. Antoniadou, A. Jannakoudakis, E. Theodoridou, Electrocatalytic reactions on carbon fibre electrodes modified by hemine II. Electro-oxidation of hydrazine, Synthetic metals, 30 (1989) 295-304.
[45] J.G. Velasco, Determination of standard rate constants for electrochemicalirreversible processes from linear sweep voltammograms, Electroanalysis, 9 (1997) 880-882.
[46] T. Łuczak, Preparation and characterization of the dopamine film electrochemically deposited on a gold template and its applications for dopamine sensing in aqueous solution, Electrochimica acta, 53 (2008) 5725-5731.