Bimetallic metal organic framework modified screen printed electrode for simultaneous voltammetric determination of calcium folinate and methotrexate
Original scientific paper
DOI:
https://doi.org/10.5599/admet.3487Keywords:
Cancer disease, chemotherapy drugs, electrochemical sensorAbstract
Background and purpose: Calcium folinate (CFT) is a medication used as an antidote to methotrexate (MTT) and as a vitamin against anaemia. MTT is used to treat a variety of carcinomas, including acute lymphoblastic leukaemia, head and neck cancer, gastric cancer, breast cancer and choriocarcinoma. Experimental approach: A nanocomposite made of Fe and Mg linked to a 1,4-benzene dicarboxylate ligand metal organic framework (FeMg-BDC MOF) was created for this investigation. Using field emission scanning electron microscopy, the morphology and structure of the Mg-BDC MOF were examined. Next, a screen-printed electrode modified with a synthetic nanocomposite (FeMg-BDC MOF/SPE) was used as the working electrode for voltammetric detection of CFT. Key results: The FeMg-BDC MOF/SPE demonstrated high electrocatalytic activity for CFT oxidation as compared to unmodified SPE. The limit of detection is 0.04 μM, and under ideal conditions, the oxidation peak currents of CFT show a linear relationship with its concentration in the range of 0.1 to 390.0 μM. Additionally, when MTT was present, the FeMg-BDC MOF/SPE demonstrated good activity toward CFT determination. The oxidation peak potentials' separation (255 mV) shows that differential pulse voltammetry may be used to detect these two medications simultaneously. Conclusion: the devised sensor's applicability was confirmed with outstanding results using CFT and MTT assays in pharmaceutical specimens and urine samples.
Downloads
References
[1] V. Reyes-Márquez, L.E. Rojas, R. Colorado-Peralta, R. Peña-Rodríguez, Ri J.M. vera-Villanueva, D. Morales-Morales. Adsorption potential of polymeric porous crystalline materials (MOFs) for the removal of Indigo carmine, Congo red, and Malachite green from water. Inorganica Chimica Acta 558 (2023) 121743. https://doi.org/10.1016/j.ica.2023.121743 DOI: https://doi.org/10.1016/j.ica.2023.121743
[2] B. Zhao, Z. Wang, K. Li, J. Huang. In situ growth of bimetallic Fe–Zn–BDC MOF on nickel foam for efficient and stable oxygen evolution Electrocatalysis. Journal of Electroanalytical Chemistry (2026) 120312. https://doi.org/10.1016/j.jelechem.2026.120312 DOI: https://doi.org/10.1016/j.jelechem.2026.120312
[3] N. Azra, V. Aziz, M.S. Nazir, S.U. Hassan, Z. Ali, M. Hussain. Fe₂O₃-integrated ZIF-67 and Cu-BTC MOF-derived photo-Fenton photocatalysts: structural engineering and enhanced imidacloprid degradation. Inorganic Chemistry Communications 189(2) (2026) 116827. https://doi.org/10.1016/j.inoche.2026.116827 DOI: https://doi.org/10.1016/j.inoche.2026.116827
[4] J.L. Liu, X.Y. Zhou, L. Qin, Y.Q. Wang, H.J. Zhu, G. Ni, M.L. Ma, M.D. Zhang. Two isostructural Ni/Co (II) MOFs based on nitrogen heterocyclic ligands and their derived carbon materials for HER performance. Journal of Molecular Structure 1252 (2022) 132184. https://doi.org/10.1016/j.molstruc.2021.132184 DOI: https://doi.org/10.1016/j.molstruc.2021.132184
[5] I. Hussain, S. Hussain, K. Singh, S. Jangra, K. Murugavel, M.R. Thalji, S. Haider, M.K. Aslam, A.C. Mendhe, P. Rosaiah, C. Park. MOF-derived phosphorus-based nanostructures for energy storage and conversion. Coordination Chemistry Reviews 565 (2026) 218114. https://doi.org/10.1016/j.ccr.2026.218114. DOI: https://doi.org/10.1016/j.ccr.2026.218114
[6] Y. Zhang, Y. Zhang, T. Hu. A porous three-dimensional Cu-MOF: Preparation and application in supercapacitors, low temperature hydrogen storage and gas separation. Inorganica Chimica Acta 575 (2025) 122414. https://doi.org/10.1016/j.ica.2024.122414 DOI: https://doi.org/10.1016/j.ica.2024.122414
[7] A. Tavousi, K. Bahrami, M. Shariati-Rad. Development of a colorimetric paper sensor based on NH2-MIL-125 MOF and bromocresol green for ammonia. Analytica Chimica Acta 1416 (2026) 345733. https://doi.org/10.1016/j.aca.2026.345733 DOI: https://doi.org/10.1016/j.aca.2026.345733
[8] Y. Tao, K. Qi, Y. Qiu, X. Guo. Multifunctional MOF-based coating on magnesium enabling integrated properties of corrosion protection, biocompatibility and stimuli-responsive drug release. Progress in Organic Coatings 216 (2026) 110228. https://doi.org/10.1016/j.porgcoat.2026.110228 DOI: https://doi.org/10.1016/j.porgcoat.2026.110228
[9] C. Yan, S. Li, T. Xu, H. Mi, Z. Wen, Sun J. Boosting initial cycling stability of α-MnO2 composite anode for lithium-ion batteries by decorated bimetallic nico-mof. Journal of Electroanalytical Chemistry 995 (2025) 119336. 10.1016/j.jelechem.2025.119336 DOI: https://doi.org/10.1016/j.jelechem.2025.119336
[10] J. Zeng, H. Zhang, A. Abuduhelili, X. Yang, F. Teng, D. Han, M. Yan, J. Sun. Highly sensitive electrochemical sensor for CD44 detection based on 3D highly conductive layers of MnLa MOF/MWCTNs. Journal of Electroanalytical Chemistry 1015 (2026) 120274. 10.1016/j.jelechem.2026.120274 DOI: https://doi.org/10.1016/j.jelechem.2026.120274
[11] M. Koli, S.P. Singh Fabrication of a magnesium MOF-engineered ultrafiltration and nanofiltration membranes for targeted removal of PFHxA, arsenic, and NOM. Desalination 619 (2025) 119559, https://doi.org/10.1016/j.desal.2025.119559 DOI: https://doi.org/10.1016/j.desal.2025.119559
[12] S. Kumar, N.K. Garg, A. Jain, A. Khopade, P. Pandey, K.K. Sawant. Nanocarriers mediated delivery of methotrexate is instrumental in treating auto-immune diseases and cancer. Journal of Drug Delivery Science and Technology 88 (2023) 104969. 10.1016/j.jddst.2023.104969 DOI: https://doi.org/10.1016/j.jddst.2023.104969
[13] A. Chakrabarti, M. Pamarthi, R. Bansal, S.S. Chakrabarti, U. Kaur. Methotrexate toxicity due to a medication dispensing error compounded by an interaction with proton pump inhibitors. Toxicology Reports 16 (2026) 102281. https://doi.org/10.1016/j.toxrep.2026.102281 DOI: https://doi.org/10.1016/j.toxrep.2026.102281
[14] B. Ferrua, G. Milano, B. Ly, J.Y. Guennec, R. Masseyeff. An enzyme immunoassay design using labelled antibodies for the determination of haptens. Application to methotrexate assay. Journal of Immunological Methods. 60 (1983) 257-268. 10.1016/0022-1759(83)90353-8 DOI: https://doi.org/10.1016/0022-1759(83)90353-8
[15] W. Cosolo, O.H. Drummer, N. Christophidis. Comparison of high-performance liquid chromatography and the Abbott fluorescent polarization radioimmunoassay in the measurement of methotrexate. Journal of Chromatography B: Biomedical Sciences and Applications 494 (1989) 201-208. https://doi.org/10.1016/S0378-4347(00)82669-9 DOI: https://doi.org/10.1016/S0378-4347(00)82669-9
[16] A.K. Yap, D.K. Luscombe. Rapid and inexpensive enzyme inhibition assay of methotrexate. Journal of pharmacological methods 16 (1986) 139-150. https://doi.org/10.1016/0160-5402(86)90019-7 DOI: https://doi.org/10.1016/0160-5402(86)90019-7
[17] S. Chen, Z. Zhang. Molecularly imprinted solid-phase extraction combined with electrochemical oxidation fluorimetry for the determination of methotrexate in human serum and urine. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 70 (2008)36-41. https://doi.org/10.1016/j.saa.2007.07.009 DOI: https://doi.org/10.1016/j.saa.2007.07.009
[18] D. Yallappa, V.K. Yuvaraaj, N. Sharma, A. Jain. RP-HPLC method for simultaneous quantification of methotrexate and quercetin in dual-drug-loaded lyotropic liquid crystalline nanoparticles: In vitro characterization and evaluation for greenness and whiteness. Microchemical Journal 220 (2025) 116684. 10.1016/j.microc.2025.116684 DOI: https://doi.org/10.1016/j.microc.2025.116684
[19] M. Shahsavani, J. Tashkhourian. Electrochemical determination of methotrexate as a chemotherapeutic agent using a ZnO-PANI nanocomposite-modified carbon paste electrode. Microchemical Journal 216 (2025) 114665. 10.1016/j.microc.2025.114665 DOI: https://doi.org/10.1016/j.microc.2025.114665
[20] N. Abbas, T.H. Kim, Ultrasensitive electrochemical detection of methotrexate in biological fluids using NiMn2O4/CNT nanocomposite-modified electrode. Sensors & Diagnostics 4 (2025) 803-814. https://doi.org/10.1039/d5sd00064e DOI: https://doi.org/10.1039/D5SD00064E
[21] V.T. Ramaekers, J.M. Sequeira, EV. Quadros. The basis for folinic acid treatment in neuro-psychiatric disorders. Biochimie 126 (2016)79-90. 10.1016/j.biochi.2016.04.005 DOI: https://doi.org/10.1016/j.biochi.2016.04.005
[22] F. Haurani, G Wang, L.M. Tocantins. Megaloblastic anemia probably caused by defective utilization of folinic acid. Blood 16 (1960) 1546-1554. https://doi.org/10.1182/blood.V16.5.1546.1546. DOI: https://doi.org/10.1182/blood.V16.5.1546.1546
[23] A. Haran, N.G. Even-Zohar, M. Haran, E. Lebel, S. Aumann, A. Shaulov, M. Gatt, B. Nachmias. Impact of folinic acid dosing on efficacy and toxicity of high-dose methotrexate in central nervous system lymphoma. Clinical Lymphoma Myeloma and Leukemia 24 (2024) 187-193. https://doi.org/10.1016/j.clml.2023.10.012 DOI: https://doi.org/10.1016/j.clml.2023.10.012
[24] I. Maesta, V.A. Silva, R.A. Costa, T.H. Carvalho, M. Branco-Silva, A. Braga, K.M. Elias, R.S. Berkowitz, N.S. Horowitz. Home-based treatment of low-risk gestational trophoblastic neoplasia with 8-day methotrexate/folinic acid. Gynecologic Oncology 204 (2026) 235-241. https://doi.org/10.1016/j.ygyno.2025.12.002 DOI: https://doi.org/10.1016/j.ygyno.2025.12.002
[25] K.O. Adeniyi, B. Osmanaj, G. Manavalan, A. Samikannu, J.P. Mikkola, B. Avni, J.F. Boily, S. Tesfalidet Engineering of layered iron vanadate nanostructure for electrocatalysis: Simultaneous detection of methotrexate and folinic acid in blood serum. Electrochimica Acta 458 (2023)142538. 10.1016/j.electacta.2023.142538 DOI: https://doi.org/10.1016/j.electacta.2023.142538
[26] R.M. Muhibes, F.A. Khazaal, Q.M. Salih, R.R. Karabat. Electrochemical determination of calcium folinate in the presence of methotrexate and 5-fluorouracil using UiO-66/CdS composite modified screen-printed carbon electrode, ADMET and DMPK 13 (2025) 2897. https://doi.org/10.5599/admet.2897. DOI: https://doi.org/10.5599/admet.2897
[27] M.A. Azzam, A. Ahmad, A.A. Labib, W.A. Mohamed, A.K. El-Sawaf, H.T. Handal. Advanced screen-printed electrodes: Shaping the future of electrochemical wastewater analysis: A review. Electrochimica Acta 561 (2026) 148646. 10.1016/j.electacta.2026.148646 DOI: https://doi.org/10.1016/j.electacta.2026.148646
[28] Z.E. Alughare, A. Sanati, Z. Esfandiari, P.J. Ahranjani. Recent advances in design, and applications of electrochemical sensors focused on green screen-printed electrodes to monitor heavy metals in food and beverage. Microchemical Journal 223 (2026) 117192. 10.1016/j.microc.2026.117192 DOI: https://doi.org/10.1016/j.microc.2026.117192
[29] K. Kamalasekaran, A.K. Sundramoorthy. Applications of chemically modified screen-printed electrodes in food analysis and quality monitoring: a review. RSC Advances 14 (2026) 27957-27971. https://doi.org/10.1039/d4ra02470b DOI: https://doi.org/10.1039/D4RA02470B
[30] S. Hong, S. Oh, E. Kim, E. Park, H.C. Chun, I.T. Kim, Y.R. Kim, Fabrication of screen-printed electrodes with long-term stability for voltammetric and potentiometric applications. Sensors and Actuators Reports 8 (2024) 100234. https://doi.org/10.1016/j.snr.2024.100234 DOI: https://doi.org/10.1016/j.snr.2024.100234
Downloads
Published
Issue
Section
License
Copyright (c) 2026 Ameer Mahmood Shaker, Batool Nassir Hamran, Ala’a R. Shaker, Hussein Ali Bahrani

This work is licensed under a Creative Commons Attribution 4.0 International License.



