Development a copper complex/ reduced graphene oxide electrode for sensitive determination of glucose in real samples

Rezaeinasab, Masoud; Rohani Moghadam, Masoud; Saeednia, Samira; Karami, Hasan

Development a copper complex/ reduced graphene oxide electrode for sensitive determination of glucose in real samples

Document Type : Original Article

Authors

Masoud Rezaeinasab

Masoud Rohani Moghadam

Samira Saeednia

Hasan Karami

Department of Chemistry, Faculty of Science, Vali-e-Asr University of Rafsanjan

Abstract

Prevention of diabetic complications and metabolic disorders, underscoring its clinical importance. In this study, a carbon paste electrode (CPE) was fabricated and functionalized with reduced graphene oxide (rGO) and Cu-L complex (Cu-L/rGO/CPE ) for electrochemical glucose sensing. Characterization via Fourier-transform infrared spectroscopy (FT-IR), Field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDX) and Raman spectroscopy confirmed the successful synthesis and integration of the rGO and Cu-L complex. Electrochemical analysis through voltammetry revealed that the modified electrode exhibited enhanced current responses toward glucose oxidation compared to the unmodified electrodes. The oxidation peak current increased proportionally with scan rate, allowing the calculation of the electron transfer coefficient (α) as 0.53. The apparent heterogeneous electron transfer rate constant (ks) was determined to be 4.27 × 10–4 s–1. Optimal catalytic activity was observed at physiological pH (~7). Modifier and nanosheets loadings were optimized at 5% and 2.5%, respectively, to maximize oxidation current. Quantitative analysis via linear sweep voltammetry (LSV) yielded a linear detection range from 5 to 90 µM, with a limit of detection (LOD) of 1.6 µM and limit of quantification (LOQ) of 4.9 µM. Chronoamperometric studies determined the glucose diffusion coefficient as 1.88 × 10–4 cm2/s. This electrode demonstrated excellent reproducibility and operational stability and validation of analytical performance in serum samples demonstrated recovery percentage of over 97%. Collectively, these findings affirm the efficacy of the Cu-L/rGO modified CPE as a sensitive and reliable electrochemical sensor for blood glucose monitoring.

Graphical Abstract

Keywords

Glucose

Sensor

Reduced graphene oxide

Modifier

Carbon paste electrode

[1] H. Sun, P. Saeedi, S. Karuranga, M. Pinkepank, K. Ogurtsova, B.B. Duncan, J.C. Mbanya, IDF Diabetes Atlas: Global, regional and country-level diabetes prevalence estimates for 2021 and projections for 2045, Diabetes Res. Clin. Pract., 183 (2022) 109119. https://doi.org/10.1016/j.diabres.2021.109119

[2] C. Chen, Q. Xie, D. Yang, H. Xiao, Y. Fu, Y. Tan, S. Yao, Recent advances in electrochemical glucose biosensors: a review, RSC Adv., 3 (2013) 4473-4491. https://doi.org/10.1039/C2RA22351A

[3] E. H. Yoo, S. Y. Lee, Glucose biosensors: an overview of use in clinical practice, Sensors, 10 (2010) 4558-4576. https://doi.org/10.3390/s100504558

[4] A. Heller, B. Feldman, Electrochemical glucose sensors and their applications in diabetes management, Chem. Rev., 108 (2008) 2482-2505. https://doi.org/10.1021/cr068069y

[5] J. Wang, Electrochemical glucose biosensors, Chem. Rev., 108 (2008) 814-825. https://doi.org/10.1021/cr068123a

[6] K.E. Toghill, R.G. Compton, Electrochemical non-enzymatic glucose sensors: a perspective and an evaluation, Int. J. Electrochem. Sci., 5 (2010) 1246-1301. https://doi.org/10.1016/S1452‑3981(23)15359‑4

[7] K. Tian, M. Prestgard, A. Tiwari, A review of recent advances in nonenzymatic glucose sensors, Mater. Sci. Eng. C, 41 (2014) 100-118. https://doi.org/10.1016/j.msec.2014.04.013

[8] M. M. Rahman, A. Ahammad, J.-H. Jin, S.J. Ahn, J. J. Lee, A comprehensive review of glucose biosensors based on nanostructured metal-oxides, Sensors, 10 (2010) 4855-4886. https://doi.org/10.3390/s100504855

[9] S. Park, H. Boo, T.D. Chung, Electrochemical non-enzymatic glucose sensors, Anal. Chim. Acta, 556 (2006) 46-57. https://doi.org/10.1016/j.aca.2005.05.080

[10] A.V. Mohan, V. Rajendran, R.K. Mishra, M. Jayaraman, Recent advances and perspectives in sweat based wearable electrochemical sensors, TrAC Trends Anal. Chem., 131 (2020) 116024. https://doi.org/10.1016/j.trac.2020.116024

[11] D.W. Hwang, S. Lee, M. Seo, T.D. Chung, Recent advances in electrochemical non-enzymatic glucose sensors–a review, Anal. Chim. Acta, 1033 (2018) 1-34. https://doi.org/10.1016/j.aca.2018.05.051

[12] M. Rezaeinasab, M. Hatefi Ardakani, R. Afsharipour, Fabrication of novel electrochemical sensor with CeO₂ nanoparticles for determination of dopamine in real samples, Colloid Nanosci. J. 3(3) (2025) 669-681 http://doi.org/10.61882/CNJ.3.3.669

[13] S.B. Bankar, M.V. Bule, R.S. Singhal, L. Ananthanarayan, Glucose oxidase—an overview, Biotechnol. Adv., 27 (2009) 489-501. https://doi.org/10.1016/j.biotechadv.2009.04.003

[14] A. Benvidi, S. Yazdanparast, M. Rezaeinasab, M. Dehghan Tezerjani, S. Abbasi, Designing and fabrication of a novel sensitive electrochemical aptasensor based on poly (L-glutamic acid)/MWCNTs modified glassy carbon electrode for determination of tetracycline, J. Electroanal. Chem. 808 (2018) 311–320. https://doi.org/10.1016/j.jelechem.2017.12.032

[15] X. Niu, M. Lan, H. Zhao, C. Chen, Highly sensitive and selective nonenzymatic detection of glucose using three-dimensional porous nickel nanostructures, Anal. Chem., 85 (2013) 3561-3569. https://doi.org/10.1021/ac3030976

[16] A. Safavi, R. Ahmadi, F.A. Mahyari, M. Tohidi, Electrocatalytic oxidation of thiourea on graphene nanosheets–Ag nanoparticles hybrid ionic liquid electrode, Sens. Actuators B, 207 (2015) 668-672. https://doi.org/10.1016/j.snb.2014.10.057

[17] M. Pasta, F. La Mantia, Y. Cui, Mechanism of glucose electrochemical oxidation on gold surface, Electrochim. Acta, 55 (2010) 5561-5568. https://doi.org/10.1016/j.electacta.2010.04.069

[18] P. Luo, F. Zhang, R.P. Baldwin, Comparison of metallic electrodes for constant-potential amperometric detection of carbohydrates, amino acids and related compounds in flow systems, Anal. Chim. Acta, 244 (1991) 169-178. https://doi.org/10.1016/S0003-2670(00)82494-0

[19] A. Benvidi, M. T. Nafar, S. Jahanbani, M. Dehghan Tezerjani,M. Rezaeinasab, S. Dalirnasab, Developing an electrochemical sensor based on a carbon paste electrode modified with nano-composite of reduced graphene oxide and CuFe2O4, nanoparticles for determination of hydrogen peroxide, Mater. Sci. Eng. C 75 (2017) 1435 –1447. https://doi.org/10.1016/j.msec.2017.03.062

[20] E. Reitz, W. Jia, M. Gentile, Y. Wang, Y. Lei, CuO nanospheres based nonenzymatic glucose sensor, Electroanalysis, 20 (2008) 2482-2486. https://doi.org/10.1002/elan.200804327

[21] X. Zhang, G. Wang, X. Liu, J. Wu, M. Li, J. Gu, B. Fang, Different CuO nanostructures: synthesis, characterization, and applications for glucose sensors, J. Phys. Chem. C, 112 (2008) 16845-16849. https://doi.org/10.1021/jp806985k

[22] Y. Mu, D. Jia, Y. He, Y. Miao, H.-L. Wu, Nano nickel oxide modified non-enzymatic glucose sensors with enhanced sensitivity, Biosens. Bioelectron., 26 (2011) 2948-2952. https://doi.org/10.1016/j.bios.2010.11.042

[23] Y. Ding, Y. Wang, L. Su, H. Zhang, Y. Lei, Preparation and characterization of NiO–Ag nanofibers for non-enzymatic glucose sensor, J. Mater. Chem., 20 (2010) 9918-9926. https://doi.org/10.1039/C0JM01968B

[24] H. Khojasteh, M. Salavati-Niasari, F.S.Sangsefidi, Photocatalytic evaluation of RGO/TiO2NWs/Pd-Ag nanocomposite as an improved catalyst for efficient dye degradation. J. Alloys Comp., 746 (2018) 611-618. https://doi.org/10.1016/j.jallcom.2018.02.345

[25] Z. H. Abdulhusain, H. A. Alshamsi, M. Salavati-Niasari, Silver and zinc oxide decorated on reduced graphene oxide: Simple synthesis of a ternary heterojunction nanocomposite as an effective visible-active photocatalyst. Int. J. Hydrogen Energy, 47(2022), 34036-34047. https://doi.org/10.1016/j.ijhydene.2022.08.018

[26] Z. H. Abdulhusain, H. A. Alshamsi, M. Salavati-Niasari, Facile synthesis of Au/ZnO/RGO nanohybrids using 1, 8-diamino-3, 6-dioxaoctan as novel functional agent for photo-degradation water treatment. J. Mater. Res.Tech., 15(2021) 6098-6112. https://doi.org/10.1016/j.jmrt.2021.11.038

[27] L.-M. Lu, L. Zhang, F.-L. Qu, H.-X. Lu, X.-B. Zhang, Z.-S. Wu, R.-Q. Yu, A nano-Ni based ultrasensitive nonenzymatic electrochemical sensor for glucose, Biosens. Bioelectron., 25 (2009) 218-223. https://doi.org/10.1016/j.bios.2009.06.041

[28] H. Bai, G. Shi, Gas sensors based on conducting polymers, Sensors, 7 (2007) 267-307. https://doi.org/10.3390/s7030267

[29] S.K. Vashist, D. Zheng, K. Al-Rubeaan, J.H. Luong, F.-S. Sheu, Advances in carbon nanotube based electrochemical sensors, Biotechnol. Adv., 29 (2011) 169-188. https://doi.org/10.1016/j.biotechadv.2010.10.002

[30] J. D. Newman, A.P. Turner, Home blood glucose biosensors: a commercial perspective, Biosens. Bioelectron., 20 (2005) 2435-2453. https://doi.org/10.1016/j.bios.2004.11.012

[31] N. Oliver, C. Toumazou, A. Cass, D. Johnston, Glucose sensors: a review of current and emerging technology, Diabet. Med., 26 (2009) 197-210. https://doi.org/10.1111/j.1464-5491.2008.02642.x

[32] S. Ferri, K. Kojima, K. Sode, Review of glucose oxidases and glucose dehydrogenases, J. Diabetes Sci. Technol., 5 (2011) 1068-1076. https://doi.org/10.1177/193229681100500507

[33] F. Tazimifar, M. Salavati-Niasari, R. Monsef, Modulating electrochemical performance of La2FeNiO6/MWCNT nanocomposites for hydrogen storage inquiries: Schiff-base ligand-assisted synthesis and characterization. Ind. Eng. Chem. Res., 64(2025), 17294-17310. https://doi.org/10.1021/acs.iecr.5c01564

[34] R. Monsef, M. Salavati-Niasari, Electrochemical sensor based on a chitosan-molybdenum vanadate nanocomposite for detection of hydroxychloroquine in biological samples. J. colloid interface sci., 613 (20220) 1-14. https://doi.org/10.1016/j.jcis.2022.01.039

[35] M. Baladi, H. Teymourinia, E. A. Dawi, M. Amiri, A. Ramazani, M. Salavati-Niasari, Electrochemical determination of imatinib mesylate using TbFeO₃/g-C₃N₄ nanocomposite modified glassy carbon electrode. Arab. J. Chem., 16(2023), 104963. https://doi.org/ 10.1016/j.arabjc.2023.104963

[36] A. A. Pouramjad, H. Khojasteh, O. Amiri, A. Khoobi, M. Salavati-Niasari, (2021). Preparation of magnetic Co₃O₄/TiO₂ nanocomposite as solid-phase microextraction fiber coupled with chromatography for detection of aromatic compounds in environmental samples. Arab. J. Chem., 14(2021), 103262. doi: 10.1016/j.arabjc.2021.103262

[37] F. Ricci, G. Palleschi, Sensor and biosensor preparation, optimisation and applications of Prussian Blue modified electrodes, Biosensors and Bioelectronics, 21 (2005) 389-407. https://doi.org/10.1016/j.bios.2004.12.001

[38] A.T. Smith, A.M. LaChance, S. Zeng, B. Liu, L. Sun, "Synthesis, properties, and applications of graphene oxide/reduced graphene oxide and their nanocomposites", Nano Materials Science, 1 (2019) 31-47. https://doi.org/10.1016/j.nanoms.2019.02.004

[39] J.C. Claussen, A. Kumar, D.B. Jaroch, M.H. Khawaja, A.B. Hibbard, D.M. Porterfield, T.S. Fisher, Nanostructuring platinum nanoparticles on multilayered graphene petal nanosheets for electrochemical biosensing, Advanced Functional Materials, 22 (2012) 3399-3405. https://doi.org/10.1002/adfm.201200551

[40] H. F. Cui, J. S. Ye, X. Liu, W. D. Zhang, F.S. Sheu, "Pt–Pb alloy nanoparticle/carbon nanotube nanocomposite: a strong electrocatalyst for glucose oxidation", Nanotechnology, 17 (2006) 2334. https:// doi 10.1088/0957-4484/17/9/043

[41] T.J. Saritha,P. Metilda, Synthesis, spectroscopic characterization and biological applications of some novel Schiff base transition metal (II) complexes derived from curcumin moiety, J. Saudi Chem. Soc., 25 (2021)101245. https://doi.org/10.1016/j.jscs.2021.101245

[42] S. Saeednia, P. Iranmanesh, M.H. Ardakani, M. Mohammadi, G. Norouzi, Phenoxo bridged dinuclear Zn (II) Schiff base complex as new precursor for preparation zinc oxide nanoparticles: Synthesis, characterization, crystal structures and photoluminescence studies, Mater. Res. Bull., 78 (2016) 1-10. https://doi.org/10.1016/j.materresbull.2016.02.010

[43] L. Liu, Z. Lin, J.-Y. Chane-Ching, H. Shao, P.-L. Taberna, P. Simon, 3D rGO aerogel with superior electrochemical performance for K–Ion battery, Energy Storage Mater., 19 (2019) 306-313. https://doi.org/10.1016/j.ensm.2019.03.013

[44] M. Malik, A. Świtlicka, A. Bieńko, U.K. Komarnicka, D.C. Bieńko, S. Kozieł, B. Machura, "Copper (ii) complexes with 2-ethylpyridine and related hydroxyl pyridine derivatives: structural, spectroscopic, magnetic and anticancer in vitro studies", RSC Adv., 12 (2022) 27648-27665. https://doi.org/10.1039/D2RA05133H

[45] I.S. Butler, J. Sedman, A. A. Ismail, FT-IR Spectra of Coordination Compounds, T. Theophanides, Ed.; Springer:Dordrecht, (1984) 83-96 https://doi.org/10.1007/978-94-009-6418-1

[46] B. Lesiak, G. Trykowski, J. Tóth, S. Biniak, L. Kövér, N. Rangam, A. Malolepszy, Chemical and structural properties of reduced graphene oxide—dependence on the reducing agent, J. Mater. Sci., 56 (2021) 3738–3754. https://doi.org/10.1007/s10853-020-05461-1

[47] J.I. Goldstein, D.E. Newbury, P. Echlin, D.C. Joy, C.E. Lyman, E. Lifshin, J.R. Michael, Image formation and interpretation, Kluwer Academic/Plenum Publish., (2003) 99–193. https://doi.org/doi: 10.1007/978-1-4615-0215-9

[48] M. Entezar Shabestari, O. Martín Cádiz, D. Díaz García, S. Gómez Ruiz, V.J. González Velázquez, J. Baselga Llidó, Facile and rapid decoration of graphene oxide with copper double salt, oxides and metallic copper as catalysts in oxidation and coupling reactions, Carbon, 161(2020) 7-16. https://doi.org/10.1016/j.carbon.2020.01.015

[49] C. Olson, R.N. Adams, Carbon paste electrodes application to anodic voltammetry, Anal. Chim. Acta, 22 (1960) 582–589. https://doi.org/10.1016/S0003-2670(00)88341-5

[50] K.H. Lubert, L. Beyer, Carbon paste electrode modified with the copper (II) complex of N-benzoyl-N′,N′-di-n-butyl-thiourea—voltammetric behavior and response to copper (II), Solvent Extr. Ion Exch., 26 (2008) 321–331. https://doi.org/10.1080/07366290802053645

[51] M. Sharp, M. Petersson, K. Edström, Preliminary determinations of electron transfer kinetics involving ferrocene covalently attached to a platinum surface, J. Electroanal. Chem. Interfacial Electrochem., 95 (1979) 123–130. https://doi.org/10.1016/S0022-0728(79)80227-2

[52] Y. Yao, Facile synthesis of copper-coated-reduced-graphene-oxide and its application as a highly sensitive electrochemical sensor for hydroquinone, J. Chem., 2022 (2022) 6894049. https://doi.org/10.1155/2022/6894049

[53] L. Berisha, A. Maloku, E. Andoni, T. Arbneshi, Electrochemical properties of modified carbon paste with copper hexacyanoferrate film on nitric oxide reduction, Am. J. Anal. Chem., 5 (2014) 308–315. http://dx.doi.org/10.4236/ajac.2014.55038

[54] A.S. Farag, Voltammetric determination of acetaminophen in pharmaceutical preparations and human urine using glassy carbon paste electrode modified with reduced graphene oxide, Anal. Sci., 38 (2022) 1213–1220. http://doi.org/10.1007/s44211-022-00150-2

[55] A. Mahmoud, M. Echabaane, K. Omri, J. Boudon, L. Saviot, N. Millot, R.B. Chaabane, Cu-doped ZnO nanoparticles for non-enzymatic glucose sensing, Molecules, 26 (2021) 929. https://doi.org/10.3390/molecules26040929

[56] Y. Zhou, W. Tang, J. Wang, G. Zhang, S. Chai, L. Zhang, T. Liu, Selective determination of dopamine and uric acid using electrochemical sensor based on poly(alizarin yellow R) film-modified electrode, Anal. Methods, 6 (2014) 3474–3481. https://doi.org/10.1039/C3AY42216J

[57] M. Rezaeinasab, A. Benvidi, M.D. Tezerjani, S. Jahanbani, A.H. Kianfar, M. Sedighipoor, An electrochemical sensor based on Ni(II) complex and multi wall carbon nanotubes platform for determination of glucose in real samples, Electroanalysis, 29 (2017) 423–432. https://doi.org/10.1002/elan.201600162

[58] S. State, L. B. Enache, P. Potorac, M. Prodana, M. Enachescu, Synthesis of copper nanostructures for non-enzymatic glucose sensors via direct-current magnetron sputtering, Nanomaterials, 12 (2022) 4144. https://doi.org/10.3390/nano12234144

[59] S. Donmez, F. Arslan, N. Sarı, E. Hasanoğlu Özkan, H. Arslan, Glucose biosensor based on immobilization of glucose oxidase on a carbon paste electrode modified with microsphere-attached L-glycine, Biotechnol. Appl. Biochem., 64 (2017) 745–753. https://doi.org/10.1002/bab.1533

[60] A. Fatoni, W. Widanarto, M.D. Anggraeni, D.W. Dwiasi, Glucose biosensor based on activated carbon–NiFe₂O₄ nanoparticles composite modified carbon paste electrode, Results Chem., 4 (2022) 100433. https://doi.org/10.1016/j.rechem.2022.100433

[61] L. J. Shang, S.-Q. Yu, X.-W. Shang, X.-Y. Wei, H.-Y. Wang, W.-S. Jiang, Q.-Q. Ren, A non-invasive glucose sensor based on 3D reduced graphene oxide-MXene and AuNPs composite electrode for the detection of saliva glucose, J. Appl. Electrochem., 54 (2024) 1807–1817. https://doi.org/10.1007/s10800-023-02065-w

[62] B.A. Hussein, A.A. Tsegaye, G. Shifera, A.M. Taddesse, A sensitive non-enzymatic electrochemical glucose sensor based on a ZnO/Co₃O₄/reduced graphene oxide nanocomposite, Sens. Diagn., 2 (2023) 347–360. https://doi.org/10.1039/d2sd00183g

Volume 3, Issue 4
Autumn 2025

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Development a copper complex/ reduced graphene oxide electrode for sensitive determination of glucose in real samples

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Volume 3, Issue 4
Autumn 2025