Electrochemical detection of chloramphenicol using gadolinium tungstate with sulphur-doped carbon nitride nanocomposite
Original scientific paper
DOI:
https://doi.org/10.5599/admet.3015Keywords:
Electrochemical sensor, antibiotic detection, cyclic voltammetry, pharmaceutical analysis, nanocompositeAbstract
Background and purpose: Chloramphenicol (CAP) is a broad-spectrum antibiotic whose unregulated presence in pharmaceuticals and food products raises significant health concerns, underscoring the need for rapid, reliable detection methods. This study aimed to develop a sensitive and economical electrochemical sensing platform based on a novel gadolinium tungstate (Gd2(WO4)3) and sulphur-doped graphitic carbon nitride (S-g-C3N4) nanocomposite for the efficient determination of CAP. Experimental approach: The Gd2(WO4)3/S-g-C3N4 nanocomposite was synthesized via a simple co-precipitation method and characterized using XRD, XPS, EDS, and TEM to confirm structural and morphological integration. A glassy carbon electrode modified with the composite was evaluated by cyclic and linear sweep voltammetry, along with analyses of interference, repeatability, stability, and real samples in eye-drop formulations and milk. Key results: The modified electrode exhibited significantly enhanced electrocatalytic oxidation of CAP compared with bare and individually modified electrodes, demonstrating high sensitivity, good selectivity against common interferents, and strong operational stability and reproducibility. A low detection limit was achieved, and the electrode effectively quantified CAP in real matrices with satisfactory recovery. Conclusion: The findings establish the Gd2(WO4)3/S-g-C3N4 nanocomposite as an efficient sensing material, offering a reliable, stable, and cost-effective platform for routine monitoring of antibiotic residues. While minor optimization may further expand its applicability, the study advances electrochemical sensing by introducing a robust nanocomposite with improved analytical performance for CAP detection.
Downloads
References
[1] T. Sun, H. Pan, Y. Mei, P. Zhang, D. Zeng, X. Liu, S. Rong, D. Chang. Electrochemical sensor sensitive detection of chloramphenicol based on ionic-liquid-assisted synthesis of de-layered molybdenum disulfide/graphene oxide nanocomposites. Journal of Applied Electrochemistry 49(3) (2019) 261-270. https://doi.org/10.1007/s10800-018-1271-6
[2] K.P. Wang, Y.C. Zhang, X. Zhang, L. Shen.Green preparation of chlorine-doped graphene and its application in electrochemical sensor for chloramphenicol detection. SN Applied Sciences 1(2) (2019) 157. https://doi.org/10.1007/s42452-019-0174-4 DOI: https://doi.org/10.1007/s42452-019-0174-4
[3] S. Gao, Y. Zhang, Z. Yang, T. Fei, S. Liu, T. Zhang. Electrochemical chloramphenicol sensors based on trace MoS₂ modified carbon nanomaterials: Insight into carbon supports. Journal of Alloys and Compounds 872 (2021) 159687. https://doi.org/10.1016/j.jallcom.2021.159687 DOI: https://doi.org/10.1016/j.jallcom.2021.159687
[4] N. Sebastian, W.C. Yu, D. Balram. Electrochemical detection of an antibiotic drug chloramphenicol based on a graphene oxide/hierarchical zinc oxide nanocomposite. Inorganic Chemistry Frontiers 6(1) (2019) 82-93. https://doi.org/10.1039/C8QI01000E DOI: https://doi.org/10.1039/C8QI01000E
[5] N. A. Shad, S. Z. Bajwa, N. Amin, A. Taj, S. Hameed, Y. Khan, Z. Dai, C. Cao, W. S. Khan. Solution growth of 1D zinc tungstate (ZnWO4) nanowires; design, morphology, and electrochemical sensor fabrication for selective detection of chloramphenicol. Journal of Hazardous Materials 367 (2019) 205-214. https://doi.org/10.1016/j.jhazmat.2018.12.072 DOI: https://doi.org/10.1016/j.jhazmat.2018.12.072
[6] M. Yadav, V. Ganesan, R. Gupta, D.K. Yadav, P.K. Sonkar. Cobalt oxide nanocrystals anchored on graphene sheets for electrochemical determination of chloramphenicol. Microchemical Journal 146 (2019) 881-887. https://doi.org/10.1016/j.microc.2019.02.025
[7] S.V. Selvi, N. Nataraj. The electro-catalytic activity of nanosphere strontium doped zinc oxide with rGO layers screen-printed carbon electrode for the sensing of chloramphenicol. Microchemical Journal 159 (2020) 105580. https://doi.org/10.1016/j.microc.2020.105580. DOI: https://doi.org/10.1016/j.microc.2020.105580
[8] G. Jaysiva, S. Manavalan, S.M. Chen, P. Veerakumar, M. Keerthi, H.S. Tu. MoN nanorod/sulfur-doped graphitic carbon nitride for electrochemical determination of chloramphenicol. ACS Sustainable Chemistry & Engineering 8(30) (2020) 11088-11098. https://doi.org/10.1021/acssuschemeng.0c00502 DOI: https://doi.org/10.1021/acssuschemeng.0c00502
[9] C. Karuppiah, K. Venkatesh, L.F. Hsu, P. Arunachalam, C.C. Yang, S.K. Ramaraj, R.J. Ramalingam, S. Aro¬kiyaraj, H.A. Al-Lohedan. An improving aqueous dispersion of polydopamine functionalized vapor grown carbon fiber for the effective sensing electrode fabrication to chloramphenicol drug detection in food samples. Microchemical Journal 170 (2021) 106675. https://doi.org/10.1016/j.microc.2021.106675 DOI: https://doi.org/10.1016/j.microc.2021.106675
[10] S. Akter Mou, R. Islam, M. Shoeb, N. Nahar. Determination of chloramphenicol in meat samples using liquid chromatography-tandem mass spectrometry. Food Science & Nutrition 9(10) (2021) 5670-5675. https://doi.org/10.1002/fsn3.2530 DOI: https://doi.org/10.1002/fsn3.2530
[11] A.E. Vilian, S.Y. Oh, M. Rethinasabapathy, R. Umapathi, S.K. Hwang, C.W. Oh, B. Park, Y.S. Huh, Y.K. Han. Improved conductivity of flower-like MnWO₄ on defect engineered graphitic carbon nitride as an efficient electrocatalyst for ultrasensitive sensing of chloramphenicol. Journal of Hazardous Materials 399 (2020) 122868. https://doi.org/10.1016/j.jhazmat.2020.122868 DOI: https://doi.org/10.1016/j.jhazmat.2020.122868
[12] Y. Baikeli, X. Mamat, F. He, X. Xin, Y. Li, H. A. Aisa, G. Hu. Electrochemical determination of chloramphenicol and metronidazole by using a glassy carbon electrode modified with iron, nitrogen co-doped nanoporous carbon derived from a metal-organic framework (type Fe/ZIF-8). Ecotoxicology and Environmental Safety 204 (2020) 111066. https://doi.org/10.1016/j.ecoenv.2020.111066 DOI: https://doi.org/10.1016/j.ecoenv.2020.111066
[13] Y.M. Xia, W. Zhang, M. Y. Li, M. Xia, L. J. Zou, W. W. Gao. Effective electrochemical determination of chloramphenicol and florfenicol based on graphene/copper phthalocyanine nanocomposites modified glassy carbon electrode. Journal of The Electrochemical Society 166(8) (2019) B654. https://iopscience.iop.org/article/10.1149/2.0801908jes/meta DOI: https://doi.org/10.1149/2.0801908jes
[14] T. Kokulnathan, S.M. Chen. Design and construction of the gadolinium oxide nanorod-embedded graphene aerogel: a potential application for electrochemical detection of postharvest fungicide. ACS Applied Materials & Interfaces 12(14) (2020) 16216-16226. https://doi.org/10.1021/acsami.9b20224. DOI: https://doi.org/10.1021/acsami.9b20224
[15] Y. Ke, Y. Sun, P. Lin, J. Zhou, Z. Xu, C. Cao, Y. Yang, S. Hu. Quantitative determination of rare earth elements in scheelite via LA-ICP-MS using REE-doped tungstate single crystals as calibration standards. Microchemical Journal 145 (2019) 642-647. https://doi.org/10.1016/j.microc.2018.11.016. DOI: https://doi.org/10.1016/j.microc.2018.11.016
[16] C. Esmaeili, M. S. Karimi, P. Norouzi, F. Wu, M. R. Ganjali, E. Safitri. Gadolinium (III) Tungstate Nanoparticles Modified Carbon Paste Electrode for Determination of Progesterone Using FFT Square-Wave Voltammetry Method. Journal of The Electrochemical Society 167(6) (2020) 067513. https://iopscience.iop.org/article/10.1149/1945-7111/ab828e/meta. DOI: https://doi.org/10.1149/1945-7111/ab828e
[17] J. Cheng, M. Wang. Preparation and electrical properties of gadolinium-doped strontium tungstate electrolyte for SOFC. Functional Materials Letters 13(03) (2020) 2050010. https://doi.org/10.1142/S1793604720500101. DOI: https://doi.org/10.1142/S1793604720500101
[18] A. Sakthivel, A. Chandrasekaran, S. Jayakumar, P. Manickam, S. Alwarappan. Sulphur doped graphitic carbon nitride as an efficient electrochemical platform for the detection of acetaminophen. Journal of The Electrochemical Society 166(15) (2019) B1461. https://doi.org/10.1149/2.0021915jes
[19] S. Vinoth, K. S. Devi, A. Pandikumar. A comprehensive review on graphitic carbon nitride based electrochemical and biosensors for environmental and healthcare applications. Trends in Analytical Chemistry 140 (2021) 116-274. https://doi.org/10.1016/j.trac.2021.116274 DOI: https://doi.org/10.1016/j.trac.2021.116274
[20] K. Kalidasan, S. Mallapur, B.B. Kulkarni, S.P. Maradur, D. Kumar, R. Deeksha, S. Kandaiah, P. Vishwa, S. Girish Kumar. Gadolinium modified g-C3N4 for S-Scheme heterojunction with monoclinic-WO3: Insights from DFT studies and related charge carrier dynamics. Journal of Materials Research and Technology 204 (2025) 166-176. https://doi.org/10.1016/j.jmst.2024.03.017 DOI: https://doi.org/10.1016/j.jmst.2024.03.017
[21] R. Zhu, Y. Zhang, X. Fang, X. Cui, J. Wang, C. Yue, W. Fang, H. Zhao, Z. Li. In situ sulfur-doped graphitic carbon nitride nanosheets with enhanced electrogenerated chemiluminescence used for sensitive and selective sensing of l-cysteine. Journal of Materials Chemistry B 7(14) (2019) 2320-2329. https://doi.org/10.1039/C9TB00301K DOI: https://doi.org/10.1039/C9TB00301K
[22] H. Starukh, P. Praus. Doping of graphitic carbon nitride with non-metal elements and its applications in photocatalysis. Catalysts 10(10) (2020) 1119. https://doi.org/10.3390/catal10101119 DOI: https://doi.org/10.3390/catal10101119
[23] A. Sakthivel, A. Chandrasekaran, S. Jayakumar, P. Manickam, S. Alwarappan. Sulphur doped graphitic carbon nitride as an efficient electrochemical platform for the detection of acetaminophen. Journal of The Electrochemical Society 166(15) (2019) B1461. https://doi.org/10.1149/2.0021915jes DOI: https://doi.org/10.1149/2.0021915jes
[24] X. Yu, Aodenggerile, Z. Jiang, J. Shen, Z. Yan, W. Li, H. Qiu. Integrating the second near-infrared fluorescence imaging with clinical techniques for multimodal cancer imaging by neodymium doped gadolinium tungstate nanoparticles. Nano Research 14 (2021) 2160-2170. https://doi.org/10.1007/s12274-020-3136-7. DOI: https://doi.org/10.1007/s12274-020-3136-7
[25] S.B. Ravikumar, T.A. Mallu, S. Subbareddy, S.A. Shivamurthy, V.D. Neelalochana, K.C. Shantakumar, J.R. Rajabathar, N. Ataollahi, S. Shadakshari. An enhanced non-enzymatic electrochemical sensor based on the Bi2S3-TiO2 nanocomposite with HNTs for the individual and simultaneous detection of 4-nitrophenol and nitrofurantoin in environmental samples. Journal of Materials Chemistry B 12(36) (2024) 9005-9017. https://doi.org/10.1039/D3TB03054G DOI: https://doi.org/10.1039/D3TB03054G
[26] V. Vinothkumar, M. Abinaya, S.M. Chen. Ultrasonic assisted preparation of CoMoO₄ nanoparticles modified electrochemical sensor for chloramphenicol determination. Journal of Solid State Chemistry 302 (2021) 122392. https://doi.org/10.1016/j.jssc.2021.122392 DOI: https://doi.org/10.1016/j.jssc.2021.122392
[27] L. Xiao, R. Xu, Q. Yuan, F. Wang. Highly sensitive electrochemical sensor for chloramphenicol based on MOF derived exfoliated porous carbon. Talanta 167 (2017) 39-43. https://doi.org/10.1016/j.talanta.2017.01.078 DOI: https://doi.org/10.1016/j.talanta.2017.01.078
[28] R. Nehru, C. D. Dong, C.W. Chen. Cobalt-doped Fe₃O₄ nanospheres deposited on graphene oxide as electrode materials for electrochemical sensing of the antibiotic drug. ACS Applied Nano Materials 4(7) (2021) 6768-6777. https://doi.org/10.1021/acsanm.1c00826. DOI: https://doi.org/10.1021/acsanm.1c00826
[29] P. Jakubec, V. Urbanová, Z. Medříková, R. Zbořil. Advanced sensing of antibiotics with magnetic gold nanocomposite: Electrochemical detection of chloramphenicol. Chemistry - A European Journal 22(40) (2016) 14279-14284. https://doi.org/10.1002/chem.201602434 DOI: https://doi.org/10.1002/chem.201602434
[30] F.Y. Kong, Y. Luo, J.W. Zhang, J.Y. Wang, W.W. Li, W. Wang. Facile synthesis of reduced graphene oxide supported Pt-Pd nanocubes with enhanced electrocatalytic activity for chloramphenicol determination. Journal of Electroanalytical Chemistry 781 (2016) 389-394. https://doi.org/10.1016/j.jelechem.2016.06.018 DOI: https://doi.org/10.1016/j.jelechem.2016.06.018
[31] M. Yadav, V. Ganesan, R. Gupta, D.K. Yadav, P.K. Sonkar. Cobalt oxide nanocrystals anchored on graphene sheets for electrochemical determination of chloramphenicol. Microchemical Journal 146 (2019) 881-887. https://doi.org/10.1016/j.microc.2019.02.025 DOI: https://doi.org/10.1016/j.microc.2019.02.025
[32] T. Sun, H. Pan, Y. Mei, P. Zhang, D. Zeng, X. Liu, S. Rong, D. Chang. Electrochemical sensor sensitive detection of chloramphenicol based on ionic-liquid-assisted synthesis of de-layered molybdenum disulfide/graphene oxide nanocomposites. Journal of Applied Electrochemistry 49(3) (2019) 261-270. https://doi.org/10.1007/s10800-018-1271-6 DOI: https://doi.org/10.1007/s10800-018-1271-6
[33] K. Giribabu, S.C. Jang, Y. Haldorai, M. Rethinasabapathy, S.Y. Oh, A. Rengaraj, Y.K. Han, W.S. Cho, C. Roh, Y.S. Huh. Electrochemical determination of chloramphenicol using a glassy carbon electrode modified with dendrite-like Fe3O4 nanoparticles. Carbon Letters 23 (2017) 38-47. https://doi.org/10.5714/CL.2017.23.038
Published
Issue
Section
License
Copyright (c) 2025 Trishul Alanahally Mallu, Gagankumar Sakleshpur Kumar, Santhosh Arehalli Shivamurthy, Nalini Seetharamaiah, Manoj Kumar Basavarajappa, Sandeep Shadakshari
This work is licensed under a Creative Commons Attribution 4.0 International License.
