Development of a rapid and sensitive electrochemical sensing assay by applying metal-organic framework/multi-walled carbon nanotubes (MOF/MWCNTs) for determination of ascorbic acid

Articles in Press

Document Type : Research Paper

Authors

1 Department of Chemistry, Ta.C., Islamic Azad University, Tabriz, Iran

2 Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz, Iran

3 Department of Chemistry, Payame Noor University, Marand, Iran

4 Department of Chemical Engineering, Ta.C., Islamic Azad University, Tabriz, Iran

10.22038/nmj.2026.85926.2153

Abstract

Objectives: L-ascorbic acid (AA, vitamin C), has important bodily functions, including immune defense, collagen formation, and metabolism. Symptoms of many diseases like cancer or cardiovascular disorders can be observed owing to maladjustment or deficiency. Hence, developing sensitive and rapid methods to determine AA in biological samples is essential. In this study, a novel electrochemical sensing assay based on Zn metal-organic framework embedded in multi-walled carbon nanotubes (Zn-MOF/MWCNTs) has been effectively developed to modify glassy carbon electrode (GCE).
Materials and Methods: Zn-MOF was synthesized using the solvothermal technique and mixed with multi-walled carbon nanotubes to obtain a modifier suspension. Various characterization methods including XRD (X-ray Diffraction), EDX (Energy-dispersive X-ray spectroscopy), HR-TEM (High-resolution transmission electron microscopy), FT-IR (Fourier-transform infrared spectroscopy), and FESEM (Field emission scanning electron microscopy) were applied to confirm the proper synthesis of Zn-MOF. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) approaches were employed to study the electrochemical behavior of the modified GCE and electrochemical determination of AA with high sensitivity.
Results: Under the optimized conditions including the drop volume, supporting electrolyte type and concentration, buffer type and concentration, and pH, the linear range and LOD (detection limit) were acquired 2–22 μM equal to 1.211 μM respectively. Moreover, other prominent analytical features including repeatability, stability, and high reproducibility were investigated for the proposed sensing platform. Additionally, the prepared sensor was effectively utilized for determination of AA in human plasma samples, attaining a recovery of 93.1%.
Conclusion: These findings clearly confirm that the developed Zn-based MOF/MWCNT sensing assay is a promising platform for accurate and effective AA determination in real biological samples, and confirms its potential for feasible biomedical applications.

Keywords

References

  1. Bettazzi F, Ingrosso C, Sfragano PS, Pifferi V, Falciola L, Curri ML, et al. Gold nanoparticles modified graphene platforms for highly sensitive electrochemical detection of vitamin C in infant food and formulae. Food Chem. 2021;344:128692.
  2. Malik M, Narwal V, Pundir C. Ascorbic acid biosensing methods: A review. Process Biochem. 2022;118:11–23.
  3. Wang H, Xie A, Li S, Wang J, Chen K, Su Z, et al. Three-dimensional g-C3N4/MWNTs/GO hybrid electrode as electrochemical sensor for simultaneous determination of ascorbic acid, dopamine and uric acid. Anal Chim Acta. 2022;1211:339907.
  4. Elgailani IEH, Elkareem M, Noh E, Adam O, Alghamdi A. Comparison of two methods for the determination of vitamin C (ascorbic acid) in some fruits. Am J Chem. 2017;2(1):1–7.
  5. Orabi AS, El-Fiky MM, Ibrahim IA, Abbas AM. Fluorescence detection of ascorbic acid in the pharmaceutical ingredient. Adv Environ Life Sci. 2023;4(1):11–22.
  6. Salkić M, Selimović A. Spectrophotometric determination of L-ascorbic acid in pharmaceuticals based on its oxidation by potassium peroxymonosulfate and hydrogen peroxide. Croat Chem Acta. 2015;88(1):73–79.
  7. Desai AP, Desai S. UV spectroscopic method for determination of vitamin C (ascorbic acid) content in different fruits in South Gujarat region. Int J Environ Sci Nat Resour. 2019;22(2):41–44.
  8. Abe C, Higuchi O, Matsumoto A, Miyazawa T. Determination of intracellular ascorbic acid using tandem mass spectrometry. Analyst. 2022;147(12):2640–2643.
  9. Moldoveanu SC. Comparison of several HPLC methods for the analysis of vitamin C. BMC. 2024;38(1):e5753.
  10. Antoce AO, Cojocaru GA, editors. Detection with flash gas chromatography electronic nose of the general influences of glutathione, ascorbic acid, tannin and carbon dioxide treatments on the volatile profiles of white wines of Feteasca Regala. BIO Web Conf. 2017: EDP Sciences. 2017: EDP Sciences.
  11. Costa BM, Prado AA, Oliveira TC, Bressan LP, Munoz RA, Batista AD, et al. Fast methods for simultaneous determination of arginine, ascorbic acid and aspartic acid by capillary electrophoresis. Talanta. 2019;204:353–358.
  12. Škugor Rončević I, Skroza D, Vrca I, Kondža AM, Vladislavić N. Development and optimization of electrochemical method for determination of vitamin C. Chemosensors. 2022;10(7):283.
  13. Habibi B, Jahanbakhshi M, Pournaghi-Azar MH. Differential pulse voltammetric simultaneous determination of acetaminophen and ascorbic acid using single-walled carbon nanotube-modified carbon–ceramic electrode. Anal Biochem. 2011;411(2):167–75.
  14. López-Pastor J-A, Martínez-Sánchez A, Aznar-Poveda J, García-Sánchez A-J, García-Haro J, Aguayo E. Quick and cost-effective estimation of vitamin C in multifruit juices using voltammetric methods. Sensors (Basel). 2020;20(3):676.
  15. Kale RA, Dhawale SC, Mulik BB, Adhikari A, Sathe BR. Polyaniline based highly selective electrochemical sensor for ascorbic acid determination: Performance studies towards real sample analysis. J Ind Eng Chem. 2024;136:167–176.
  16. Zestos AG. Carbon nanoelectrodes for the electrochemical detection of neurotransmitters. Int J Electrochem. 2018;2018:3679627.
  17. Hsieh H-H, Xu J-Y, Lin J-T, Chiang Y-T, Weng Y-C. Graphene–Multiwalled Carbon Nanotubes Modified Glassy Carbon Electrodes for Simultaneous Detection of Ascorbic Acid, Dopamine, and Uric Acid. ACS omega. 2025;10(8):8160–8171.
  18. Sohrabi H, Majidi MR, Nami F, Asadpour-Zeynali K, Khataee A, Mokhtarzadeh A. A novel engineered label-free Zn-based MOF/CMC/AuNPs electrochemical genosensor for highly sensitive determination of Haemophilus Influenzae in human plasma samples. Microchim. Acta. 2021;188(3):100.
  19. Liu D, Lu K, Poon C, Lin W. Metal–organic frameworks as sensory materials and imaging agents. Inorg. Chem. 2014;53(4):1916–1924.
  20. Liu Z, He W, Guo Z. Metal coordination in photoluminescent sensing. Chem Soc Rev. 2013;42(4):1568–1600.
  21. Lustig WP, Mukherjee S, Rudd ND, Desai AV, Li J, Ghosh SK. Metal–organic frameworks: functional luminescent and photonic materials for sensing applications. Chem Soc Rev. 2017;46(11):3242–3285.
  22. Li Y, Jiang K, Zhang J, Xia T, Cui Y, Yang Y, et al. A turn-on fluorescence probe based on post-modified metal–organic frameworks for highly selective and fast-response hypochlorite detection. Polyhedron. 2018;148:76–80.
  23. Li Y, Xia T, Zhang J, Cui Y, Li B, Yang Y, et al. A manganese-based metal-organic framework electrochemical sensor for highly sensitive cadmium ions detection. J Solid State Chem. 2019;275:38–42.
  24. Li Y, Zhang X, Zhang L, Jiang K, Cui Y, Yang Y, et al. A nanoscale Zr-based fluorescent metal-organic framework for selective and sensitive detection of hydrogen sulfide. J. Solid State Chem. 2017;255:97–101.
  25. Sohrabi H, Majidi MR, Asadpour-Zeynali K, Khataee A, Mokhtarzadeh A. Bimetallic Fe/Mn MOFs/MβCD/AuNPs stabilized on MWCNTs for developing a label-free DNA-based genosensing bio-assay applied in the determination of Salmonella typhimurium in milk samples. Chemosphere. 2022;287:132373.
  26. Schoedel A, Li M, Li D, O’Keeffe M, Yaghi OM. Structures of metal–organic frameworks with rod secondary building units. Chem. Rev. 2016;116(19):12466–12535.
  27. Bilal S, Akbar A, Shah A-u-HA. Highly selective and reproducible electrochemical sensing of ascorbic acid through a conductive polymer coated electrode. Polymers. 2019;11(8):1346.
  28. Huang D, Li X, Chen M, Chen F, Wan Z, Rui R, et al. An electrochemical sensor based on a porphyrin dye-functionalized multi-walled carbon nanotubes hybrid for the sensitive determination of ascorbic acid. J. Electroanal. Chem. 2019;841:101–106.
  29. Song J, Xu L, Xing R, Li Q, Zhou C, Liu D, et al. Synthesis of Au/graphene oxide composites for selective and sensitive electrochemical detection of ascorbic acid. SciRep.  2014;4(1):7515.
  30. Peik-See T, Pandikumar A, Nay-Ming H, Hong-Ngee L, Sulaiman Y. Simultaneous electrochemical detection of dopamine and ascorbic acid using an iron oxide/reduced graphene oxide modified glassy carbon electrode. Sensors. (Basel). 2014;14(8):15227–15243.
  31. Bouali W, Erk N, Genc AA, Ahmed HEH, Soylak M. A new and powerful electrochemical sensing platform based on MWCNTs@ Fe3O4@ CuAl2O4 for the determination of the anticancer agent Alpelisib in bulk and biological fluids. Microchem J. 2023;195:109478.
  32. Li Y, Ye W, Cui Y, Li B, Yang Y, Qian G. A metal-organic frameworks@ carbon nanotubes based electrochemical sensor for highly sensitive and selective determination of ascorbic acid. J Mol Struct. 2020;1209:127986.
  33. Omkaramurthy B, Krishnamurthy G, Prasad N. Two new Zn (II) bdc Metal-Organic Frameworks based on benzene 1, 4-dicarboxylic acid: Synthesis, Crystal structures, Luminescent properties and Electrochemical studies. Mater Today Proc. 2020;22:2179–2190.
  34. Nazari Z, Taher MA, Fazelirad H. A Zn based metal organic framework nanocomposite: synthesis, characterization and application for preconcentration of cadmium prior to its determination by FAAS. RSC Adv. 2017;7(71):44890–44895.
  35. Rageh HM, Abou-Krisha M, Abo-Bakr A, Abd-Elsabour M. Electrochemical Behavior and the Detection Limit of Ascorbic Acid on a Pt Modified Electrode. IntJ Electrochem Sci. 2014;10:4105–4115.
Nanomedicine Journal

Articles in Press, Accepted Manuscript
Available Online from 09 June 2026

Files

Share

How to cite

Statistics