Electrochemical determination of paracetamol and chlorpheniramine  using AuNPs-rGO modified glassy carbon electrode

Original scientific paper

Authors

DOI:

https://doi.org/10.5599/jese.2841

Keywords:

Drug sensors, square-wave anodic stripping voltammetry, ochemically reduced graphene oxide, herbal medicine

Abstract

One of the significant durability challenges is the corrosion of reinforced concrete. A gold nanoparticle/reduced graphene oxide modified glassy carbon electrode (AuNPs-rGO-GCE) was fabricated using an electrochemical reduction method for the simultaneous determination of paracetamol (PAR) and chlorpheniramine maleate (CPM). AuNPs-rGO modified GC electrodes were prepared through direct electrochemical reduction of GO to rGO, followed by direct reduction of Au ions to Au on the rGO matrix. X-ray diffraction, scanning electron microscopy, Fourier-transform infrared spectra, Raman spectroscopy, energy dispersive X-ray spectroscopy, high-resolution transmission electron microscopy, electrochemical impedance spectroscopy, and X-ray photoelectron spectroscopy characterized the resulting AuNPs-rGO. It was found that AuNPs around 15.4 nm were highly dispersed on the rGO. The modification of GCE by AuNPs-rGO accelerates the electron transfer process and increases the conductivity of the electrode. The AuNPs-rGO modified electrode was used to simultaneously determine PAR and CPM using the square-wave anodic stripping voltammetry (SQW-ASV) method. Under suitable experimental conditions, the SQW-ASV method using AuNPs-rGO-GCE showed a wide linear range from 23.7 to 140.0 µM for PAR and from 7.5 to 54.0 µM for CPM. The limit of detection of PAR and CPM was 7.12 and 2.54 µM, respectively. The proposed SQW-ASV method was applied to analyze PAR and CPM in samples of herbal medicine simultaneously, and the results were compared with those of high-performance liquid chromatography, with no statistical difference.

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References

National Health Service, Paracetamol for adults, 2018, https://www.nhs.uk/medicines/paracetamol-for-adults/. (date accessed: May 18, 2024)

[2] D. N. Bateman, J. W. Dear, H. K. Thanacoody, S. H. Thomas, M. Eddleston, E. A. Sandilands, J. Coyle, J. G. Cooper, A. Rodriguez, I. Butcher, S. C. Lewis, A. D. Vliegenthart, A. Veiraiah, D. J. Webb, A. Gray, Reduction of adverse effects from intravenous acetylcysteine treatment for paracetamol poisoning: a randomised controlled trial, Lancet 383 (2014) 697-704. https://doi.org/10.1016/s0140-6736(13)62062-0 DOI: https://doi.org/10.1016/S0140-6736(13)62062-0

[3] Ç. Tas, Y. Özkan, A. Savaser, T. Baykara, In vitro release studies of chlorpheniramine maleate from gels prepared by different cellulose derivatives, Il Farmaco 58 (2003) 605-611. https://doi.org/10.1016/S0014-827X(03)00080-6 DOI: https://doi.org/10.1016/S0014-827X(03)00080-6

[4] S. Y. Yang, J. S. Byun, J. H. Hwang, J. J. An, K. E. Hong, W. Kang, Y. K. Lee, Y. . Park, Study of In¬struments for Assessment and Clinical Research Trends in Common Cold, The Journal of Kore¬an Medicine 29 (2008) 165-181 https://koreascience.kr/article/JAKO200817963246474.pdf

[5] S. S. Nitin Borkar, Review of Simultaneous determination of analytes by High Performance Liquid Chromatography (HLPC) in multicomponent cough and cold oral drug products., International Journal of PharmTech Research 3 (2011) 1339-1345 https://www.researchgate.net/publication/266370935

[6] M. F. H. Al-Samarrai, M. Z. Lafta, M. J. T. Al-Abbasee, O.J. Muhammad, Development and Validation of a RP-HPLC Method for Simultaneous Quantification of Paracetamol and Phenylephrine Hydrochloride, International Journal of Design & Nature and Ecodynamics 19 (2024) 275-280. https://doi.org/10.18280/ijdne.190130 DOI: https://doi.org/10.18280/ijdne.190130

[7] A. Arage, T. Layloff, A. Hymete, A. Ashenef, High performance thin layer chromatography (HPTLC) method development and validation for the simultaneous determination of paracetamol, caffeine, chlorpheniramine and phenylepherine in tablet formulation, Acta Chromatographica 35 (2023) 170-178. https://doi.org/10.1556/1326.2022.01028 DOI: https://doi.org/10.1556/1326.2022.01028

[8] M. A. Mohamed, Stability-Indicating New RP-UPLC Method for Simultaneous Determination of a Quaternary Mixture of Paracetamol, Pseudoephedrine, Chlorpheniramine, and Sodium Benzoate in (Cold–Flu) Syrup Dosage Form, Journal of AOAC International 105 (2022) 703-716. https://doi.org/10.1093/jaoacint/qsac002 DOI: https://doi.org/10.1093/jaoacint/qsac002

[9] L. C. D. Chawe, N. K. Tittikpina, S. M. Ndiaye, B. N. Amadou Diop, D. Fall, Y. M. Diop, S. O. Sarr, Validation of an UV-Visible spectrophotometry assay method for the determination of chlorpheniramine maleate tablets without prior extraction, International Journal of Biological and Chemical Sciences 15 (2021) 273-281. https://doi.org/10.4314/ijbcs.v15i1.24 DOI: https://doi.org/10.4314/ijbcs.v15i1.24

[10] United States Pharmacopeia and National Formulary, USP 43 – NF 38, Rockville, MD: United States Pharmacopeial Convention, USA, 2020. http://182.160.97.198:8080/xmlui/handle/123456789/1493

[11] M. Stoytcheva, Z. Velkova, V. Gochev, B. Valdez, M. Curiel, Advances in electrochemical sensors for paracetamol detection: Electrode materials, modifications, and analytical applications, International Journal of Electrochemical Science 20 (2025) 100924. https://doi.org/10.1016/j.ijoes.2024.100924 DOI: https://doi.org/10.1016/j.ijoes.2024.100924

[12] H. asadollahzadeh, Developing an electrochemical sensor based on a carbon paste electrode modified with ZnO nanoparticles synthesized by microwave for determination of chlorphe-niramine maleate, Analytical Methods in Enviromental Chemistry Journal 4 (2021) 16-25. https://doi.org/10.24200/amecj.v4.i01.130 DOI: https://doi.org/10.24200/amecj.v4.i01.130

[13] A. Samadi-Maybodi, S. K. Hassaninejad-Darzi, H. Nejad-Darzi, H. Ilkhani, A New Sensor for Determination of Paracetamol, Phenylephrine Hydrochloride and Chlorpheniramine Maleate in Pharmaceutical Samples Using Nickel Phosphate Nanoparticles Modified Carbon Past Electrode, Analytical and Bioanalytical Electrochemistry 3 (2011) 134-145 https://www.researchgate.net/publication/234166408

[14] N. Fairley, V. Fernandez, M. Richard‐Plouet, C. Guillot-Deudon, J. Walton, E. Smith, D. Flahaut, M. Greiner, M. Biesinger, S. Tougaard, D. Morgan, J. Baltrusaitis, Systematic and collaborative approach to problem solving using X-ray photoelectron spectroscopy, Applied Surface Science Advances 5 (2021) 100112. https://doi.org/https://doi.org/10.1016/j.apsadv.2021.100112 DOI: https://doi.org/10.1016/j.apsadv.2021.100112

[15] W. S. Hummers Jr., R. E. Offeman, Preparation of Graphitic Oxide, Journal of the American Chemical Society 80 (1958) 1339-1339. https://doi.org/10.1021/ja01539a017 DOI: https://doi.org/10.1021/ja01539a017

[16] D. C. Marcano, D. V. Kosynkin, J. M. Berlin, A. Sinitskii, Z. Sun, A. Slesarev, L. B. Alemany, W. Lu, J. M. Tour, Improved Synthesis of Graphene Oxide, ACS Nano 4 (2010) 4806-4814. https://doi.org/10.1021/nn1006368 DOI: https://doi.org/10.1021/nn1006368

[17] S. Cheemalapati, S. Palanisamy, S.-M. Chen, Electrochemical Determination of Isoniazid at Electrochemically reduced graphene oxide modified Electrode, International Journal of Elec-tro¬chemical Science 8 (2013) 3953-3962. https://doi.org/10.1016/S1452-3981(23)14444-0 DOI: https://doi.org/10.1016/S1452-3981(23)14444-0

[18] Y.-H. Chen, R. Kirankumar, C.-L. Kao, P.-Y. Chen, Electrodeposited Ag, Au, and AuAg nanoparticles on graphene oxide-modified screen-printed carbon electrodes for the voltammetric determination of free sulfide in alkaline solutions, Electrochimica Acta 205 (2016) 124-131. https://doi.org/10.1016/j.electacta.2016.04.111 DOI: https://doi.org/10.1016/j.electacta.2016.04.111

[19] U. Koelle, A. Laguna, Electrochemistry of Au-complexes, Inorganica Chimica Acta 290 (1999) 44-50. https://doi.org/10.1016/S0020-1693(99)00112-7 DOI: https://doi.org/10.1016/S0020-1693(99)00112-7

[20] S. Y. Toh, K. S. Loh, S. K. Kamarudin, W. R. W. Daud, Graphene production via electrochemical reduction of graphene oxide: Synthesis and characterisation, Chemical Engineering Journal 251 (2014) 422-434. https://doi.org/10.1016/j.cej.2014.04.004 DOI: https://doi.org/10.1016/j.cej.2014.04.004

[21] Y. Xu, M. Gao, G. Zhang, X. Wang, J. Li, S. Wang, Y. Sang, Electrochemically reduced graphene oxide with enhanced electrocatalytic activity toward tetracycline detection, Chinese Journal of Catalysis 36 (2015) 1936-1942. https://doi.org/10.1016/S1872-2067(15)60956-1 DOI: https://doi.org/10.1016/S1872-2067(15)60956-1

[22] P. E. Rider, K. A. Gschneidner Jr., O.D. McMasters, Gold-rich rare-earth-gold solid solutions, Transactions of the Metallurgical Society of AIME 233 (1965) 1488-1496. https://www.osti.gov/biblio/4616986

[23] S. Z. Bas, Gold nanoparticle functionalized graphene oxide modified platinum electrode for hydrogen peroxide and glucose sensing, Materials Letters 150 (2015) 20-23. https://doi.org/10.1016/j.matlet.2015.02.130 DOI: https://doi.org/10.1016/j.matlet.2015.02.130

[24] P. K. Sahoo, S. Sahoo, A. K. Satpati, D. Bahadur, Solvothermal synthesis of reduced graphene oxide/Au nanocomposite-modified electrode for the determination of inorganic mercury and electrochemical oxidation of toxic phenolic compounds, Electrochimica Acta 180 (2015) 1023-1032. https://doi.org/10.1016/j.electacta.2015.09.018 DOI: https://doi.org/10.1016/j.electacta.2015.09.018

[25] S. Stankovich, D. A. Dikin, R. D. Piner, K. A. Kohlhaas, A. Kleinhammes, Y. Jia, Y. Wu, S. T. Ngu¬yen, R. S. Ruoff, Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide, Carbon 45 (2007) 1558-1565. https://doi.org/10.1016/j.carbon.2007.02.034 DOI: https://doi.org/10.1016/j.carbon.2007.02.034

[26] K. Ghanbari, A. Hajian, Electrochemical characterization of Au/ZnO/PPy/RGO nanocomposite and its application for simultaneous determination of ascorbic acid, epinephrine, and uric acid, Journal of Electroanalytical Chemistry 801 (2017) 466-479. https://doi.org/10.1016/j.jelechem.2017.07.024 DOI: https://doi.org/10.1016/j.jelechem.2017.07.024

[27] Y. Qin, J. Li, Y. Kong, X. Li, H. Xue, In Situ Synthesis of Photoreduced Au Nanoclusters Deco-rated-Graphene Hybrid as a High Efficient Electrocatalyst, Journal of The Electrochemical Society 161 (2014) H172. https://doi.org/10.1149/2.025404jes DOI: https://doi.org/10.1149/2.025404jes

[28] M. Turner, V. B. Golovko, O. P. Vaughan, P. Abdulkin, A. Berenguer-Murcia, M. S. Tikhov, B. F. Johnson, R. M. Lambert, Selective oxidation with dioxygen by gold nanoparticle catalysts derived from 55-atom clusters, Nature 454 (2008) 981-983. https://doi.org/10.1038/nature07194 DOI: https://doi.org/10.1038/nature07194

[29] Z. Song, W. Li, F. Niu, Y. Xu, L. Niu, W. Yang, Y. Wang, J. Liu, A novel method to decorate Au clusters onto graphene via a mild co-reduction process for ultrahigh catalytic activity, Journal of Materials Chemistry A 5 (2017) 230-239. https://doi.org/10.1039/C6TA08284J DOI: https://doi.org/10.1039/C6TA08284J

[30] J. Wang, Analytical Electrochemistry, John Wiley & Sons, USA, 2006. https://doi.org/10.1002/0471790303 DOI: https://doi.org/10.1002/0471790303

[31] A. J. Bard, L. R. Faulkner, Electrochemical methods: fundamentals and applications, John Wiley & Sons, USA, 2001. ISBN 0-471-04372-9

[32] A. J. S. Ahammad, T. Islam, M. M. Hasan, M. N. I. Mozumder, R. Karim, N. Odhikari, P. R. Pal, S. Sarker, D. M. Kim, Reduced Graphene Oxide Screen-Printed FTO as Highly Sensitive Electrodes for Simultaneous Determination of Dopamine and Uric Acid, Journal of The Electrochemical Society 165 (2018) B174. https://doi.org/10.1149/2.0121805jes DOI: https://doi.org/10.1149/2.0121805jes

[33] Y. Pang, Y. Zhang, X. Sun, H. Ding, T. Ma, X. Shen, Synergistical accumulation for electrochemical sensing of 1-hydroxypyrene on electroreduced graphene oxide electrode, Talanta 192 (2019) 387-394. https://doi.org/10.1016/j.talanta.2018.08.042 DOI: https://doi.org/10.1016/j.talanta.2018.08.042

[34] E. Murugan, P. Arumugam, M. Kesava, A. Vinitha, Synthesis and characterization of graphene nanosheets for electrochemical quantification of chlorpheniramine maleate drugs using a modified glassy carbon electrode, Indian Journal of Chemical Technology 29 (2022) 713-720. https://doi.org/10.56042/ijct.v29i6.67423 DOI: https://doi.org/10.56042/ijct.v29i6.67423

[35] S. I. Khan, R. V. Motghare, Electrochemical Determination of Chlorophenaramine Based on RTIL/CNT Composite Modified Glassy Carbon Electrode in Pharmaceutical Samples, Journal of The Electrochemical Society 166 (2019) B1202. https://doi.org/10.1149/2.0911913jes DOI: https://doi.org/10.1149/2.0911913jes

[36] M. Amiri, M. Alimoradi, K. Nekoueian, A. Bezaatpour, Cobalt Flower-like Nanostructure as Modifier for Electrocatalytic Determination of Chloropheniramine, Industrial & Engineering Chemistry Research 51 (2012) 14384-14389. https://doi.org/10.1021/ie3016736 DOI: https://doi.org/10.1021/ie3016736

[37] A. S. Rajpurohit, A. K. Srivastava, Simultaneous electrochemical sensing of three prevalent anti-allergic drugs utilizing nanostructured manganese hexacyanoferrate/chitosan modified screen printed electrode, Sensors and Actuators B 294 (2019) 231-244. https://doi.org/10.1016/j.snb.2019.05.046 DOI: https://doi.org/10.1016/j.snb.2019.05.046

[38] D. E. Bayraktepe, Z. Yazan, Two-layered Au@Ag Bimetallic Nanocomposites-poly (L-Met) Platform for Highly Sensitive Chlorpheniramine Maleate Detection, Electroanalysis 34 (2022) 445-454. https://doi.org/10.1002/elan.202100422 DOI: https://doi.org/10.1002/elan.202100422

[39] N. Shetti, D. Nayak, Electrochemical detection of chlorpheniramine maleate in the presence of an anionic surfactant and its analytical applications, Canadian Journal of Chemistry 95 (2017) 553-559. https://doi.org/10.1139/cjc-2016-0406 DOI: https://doi.org/10.1139/cjc-2016-0406

[40] P. Pinyou, V. Blay, J. Pansalee, S. Ramkrathok, T. Phetmuenwai, J. Jakmunee, K. Chansaenpak, S. Lisnund, Co-deposition of Graphene Oxide and Silver Nanoparticles for the Voltammetric Sensing of Chlorpheniramine, Electrocatalysis 14 (2023) 648-658. https://doi.org/10.1007/s12678-023-00826-x DOI: https://doi.org/10.1007/s12678-023-00826-x

[41] T. C. Pereira, N. R. Stradiotto, Electrochemical sensing of lactate by using an electrode modified with molecularly imprinted polymers, reduced graphene oxide and gold nanoparticles, Microchimica Acta 186 (2019) 764. https://doi.org/10.1007/s00604-019-3898-3 DOI: https://doi.org/10.1007/s00604-019-3898-3

[42] S. D. Lamani, R. N. Hegde, A. P. Savanur, S. T. Nandibewoor, Voltammetric Determination of Chlorpheniramine Maleate Based on the Enhancement Effect of Sodium-dodecyl Sulfate at Carbon Paste Electrode, 23 (2011) 347-354. https://doi.org/10.1002/elan.201000369 DOI: https://doi.org/10.1002/elan.201000369

[43] D. A. C. Brownson, C. E. Banks, The Handbook of Graphene Electrochemistry, Springer-Verlag London Ltd., 2014. https://doi.org/10.1007/978-1-4471-6428-9 DOI: https://doi.org/10.1007/978-1-4471-6428-9

[44] J. Soleymani, M. Hasanzadeh, N. Shadjou, M. Khoubnasab Jafari, J.V. Gharamaleki, M. Yadollahi, A. Jouyban, A new kinetic–mechanistic approach to elucidate electrooxidation of doxorubicin hydrochloride in unprocessed human fluids using magnetic graphene based nanocomposite modified glassy carbon electrode, Materials Science and Engineering C 61 (2016) 638-650. https://doi.org/10.1016/j.msec.2016.01.003 DOI: https://doi.org/10.1016/j.msec.2016.01.003

[45] M. A. Raj, S. A. John, Fabrication of Electrochemically Reduced Graphene Oxide Films on Glassy Carbon Electrode by Self-Assembly Method and Their Electrocatalytic Application, The Journal of Physical Chemistry C 117 (2013) 4326-4335. https://doi.org/10.1021/jp400066z DOI: https://doi.org/10.1021/jp400066z

[46] W. Horwitz, R. Albert, Quality IssuesThe Concept of Uncertainty as Applied to Chemical Measurements, Analyst 122 (1997) 615-617. https://doi.org/10.1039/A703178E DOI: https://doi.org/10.1039/a703178e

[47] P. Konieczka, Quality Assurance and Quality Control in the Analytical Chemical Laboratory, CRC Press Taylor & Francis Group, 2018, https://doi.org/10.1201/9781315295015 DOI: https://doi.org/10.1201/9781315295015

[48] J. N. Miller, J. C. Miller, R. D. Miller, Statistics and Chemometrics for Analytical Chemistry, Pearson Education Limited, UK, 2018. https://api.pageplace.de/preview/DT0400.9781292186726_A36382216/preview-9781292186726_A36382216.pdf

[49] D. Eskiköy Bayraktepe, E. K. İnal, Z. Yazan, Preparation and characterization of a pencil graphite electrode modified with gold nanoparticles decorated poly (l-methionine) and its use in the simultaneous sensitive electrochemical analysis of ascorbic acid, acetaminophen, chlorpheniramine maleate, and caffeine, Microchemical Journal 171 (2021) 106812. https://doi.org/10.1016/j.microc.2021.106812 DOI: https://doi.org/10.1016/j.microc.2021.106812

[50] M. Perez-Ortiz, P. Pizzaro, A. Álvarez-Lueje, Carbon nanotubes–ionic liquid gel. characterization and application to pseudoephedrine and chlorpheniramine determination in pharmaceuticals, Journal of the Chilean Chemical Society 64 (2019) 4323-4331. https://doi.org/10.4067/s0717-97072019000104324 DOI: https://doi.org/10.4067/s0717-97072019000104324

[51] Z. Pourghobadi, R. Pourghobadi, Electrochemical Behavior and Voltammetric Determination of Chlorpheniramine Maleate by Means of Multiwall Carbon Nanotubes-Modified Glassy Carbon Electrode, International Journal of Electrochemical Science 10 (2015) 7241-7250. https://doi.org/10.1016/S1452-3981(23)17345-7 DOI: https://doi.org/10.1016/S1452-3981(23)17345-7

[52] E. A. Khudaish, M. Al-Hinaai, S. Al-Harthy, K. Laxman, Electrochemical oxidation of chlorpheniramine at polytyramine film doped with ruthenium (II) complex: Measurement, kinetic and thermodynamic studies, Electrochimica Acta 135 (2014) 319-326. https://doi.org/10.1016/j.electacta.2014.05.029 DOI: https://doi.org/10.1016/j.electacta.2014.05.029

[53] B. Magnusson, U. Örnemark, Eurachem Guide: The Fitness for Purpose of Analytical Methods – A Laboratory Guide to Method Validation and Related Topics, 2014. ISBN 978-91-87461-59-0

[54] AOAC International, Appendix F: Guidelines for Standard Method Performance Requirements, 2016, https://www.aoac.org/wp-content/uploads/2019/08/app_pdf

[55] Y. Liu, B. Zhu, M. Xue, Z. Jiang, X. Guo, Studies on the chiral separation of pheniramine and its enantioselective pharmacokinetics in rat plasma by HPLC-MS/MS, Microchemical Journal 156 (2020) 104989. https://doi.org/10.1016/j.microc.2020.104989 DOI: https://doi.org/10.1016/j.microc.2020.104989

[56] P. Butmee, G. Tumcharern, G. Thouand, K. Kalcher, A. Samphao, An ultrasensitive immunosensor based on manganese dioxide-graphene nanoplatelets and core shell Fe3O4@Au nanoparticles for label-free detection of carcinoembryonic antigen, Bioelectrochemistry 132 (2020) 107452. https://doi.org/10.1016/j.bioelechem.2019.107452 DOI: https://doi.org/10.1016/j.bioelechem.2019.107452

[57] Ministry of Health, Regulations on the list of prohibited substances used in the production and trading of health protection foods, Viet Nam, 2021, https://thuvienphapluat.vn/van-ban/The-thao-Y-te/Thong-tu-10-2021-TT-BYT-Danh-muc-chat-cam-su-dung-san-xuat-thuc-pham-bao-ve-suc-khoe-481014.aspx

[58] Q. Hu, Y-I Cui, K. Wang, S. Ji, Detection of 16 anti-inflammatory and anti-histamine chemical drugs added illegally into traditional Chinese medicine and health food by liquid chromatography-ion trap mass spectrometry method, Chinese Journal of Pharmaceutical Analysis 12 (2008) 2065-2068. https://www.ingentaconnect.com/content/jpa/cjpa/2008/00000028/00000012/art00022

[59] J. Y. Kim, J. Y. Choi, C. Y. Yoon, S. Cho, W. S. Kim, J. A. Do, LC–MS/MS monitoring of 22 illegal antihistamine compounds in health food products from the Korean market, Journal of the Korean Society for Applied Biological Chemistry 58 (2015) 137-147. https://doi.org/10.1007/s13765-015-0004-3 DOI: https://doi.org/10.1007/s13765-015-0004-3

[60] A. Nili-Ahmadabadi, Z. Borzouee, D. Ahmadimoghaddam, F. Firozian, D. Dastan, The occurrence of acetaminophen/codeine as an adulterant in herbal analgesic supplements in Hamadan, Iran: A pilot study, Complementary Therapies in Medicine 42 (2019) 223-225. https://doi.org/10.1016/j.ctim.2018.11.018 DOI: https://doi.org/10.1016/j.ctim.2018.11.018

Published

25-08-2025

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Section

Electroanalytical chemistry

How to Cite

Electrochemical determination of paracetamol and chlorpheniramine  using AuNPs-rGO modified glassy carbon electrode: Original scientific paper. (2025). Journal of Electrochemical Science and Engineering, 15(6), Article 2841. https://doi.org/10.5599/jese.2841

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