Abstract
Three different types of Zr-based MOFs derived from benzene dicarboxylic acid (BDC) and naphthalene dicarboxylic acid as organic linkers (ZrBDC, 2,6-ZrNDC, and 1,4-ZrNDC) were synthesized. They were characterized using X-ray diffraction analysis (XRD), X-ray photoelectron spectroscopy (XPS), Fourier-transform IR spectroscopy (FT-IR), and Transmission electron microscopy (TEM). Their hydrophilic/hydrophobic nature was investigated via contact angle measurements; ZrBDC MOF was hydrophilic and the other two (ZrNDC) MOFs were hydrophobic. The three MOFs were combined with MWCNTs as electrode modifiers for the determination of a hydrophobic analyte, flibanserin (FLB), as a proof-of-concept analyte. Under the optimized experimental conditions, a significant enhancement in the oxidation peak current of FLB was observed when utilizing 2,6-ZrNDC and 1,4-ZrNDC, being the highest when using 1,4-ZrNDC. Furthermore, a thorough investigation of the complex oxidation pathway of FLB was performed by carrying out simultaneous spectroelectrochemical measurements. Based on the obtained results, it was verified that the piperazine moiety of FLB is the primary site for electrochemical oxidation. The fabricated sensor based on 1,4-ZrNDC/MW/CPE showed an oxidation peak of FLB at 0.8 V vs Ag/AgCl. Moreover, it showed excellent linearity for the determination of FLB in the range 0.05 to 0.80 μmol L−1 with a correlation coefficient (r) = 0.9973 and limit of detection of 3.0 nmol L−1. The applicability of the developed approach was demonstrated by determination of FLB in pharmaceutical tablets and human urine samples with acceptable repeatability (% RSD values were below 1.9% and 2.1%, respectively) and reasonable recovery values (ranged between 97 and 103% for pharmaceutical tablets and between 96 and 102% for human urine samples). The outcomes of the suggested methodology can be utilized for the determination of other hydrophobic compounds of pharmaceutical or biological interest with the aim of achieving low detection limits of these compounds in various matrices.
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Acknowledgements
The authors would like to express their sincere thanks to Prof. Hossieny Ibrahim (Professor of Electroanalytical Chemistry, Department of Chemistry, Faculty of Science, Assiut University, Assiut, Egypt) for helping the authors in setting up the SEC apparatus and designing the connections to SEC and electrochemical cells.
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The authors would like to thank the German Federal Ministry for Economic Cooperation and Development (BMZ) for funding the purchase and donation of the Gamry Interface 1010E Potentiostat/Galvanostat/ZRA model and Flame S-UV–VIS spectrometer (with the connected accessories) via the German Academic Exchange Service (Deutscher Akademischer Austauschdienst – DAAD), Bohn, Germany.
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Azza H. Rageh: conceptualization, funding acquisition, data curation, formal analysis, validation, investigation, methodology, writing—original draft, and writing—review and editing. Mohamed I. Said: conceptualization, funding acquisition, data curation, formal analysis, validation, investigation, methodology, writing—original draft and writing—review and editing. Fatma. A.M. Abdela-aal: conceptualization, funding acquisition, data curation, formal analysis validation, investigation, methodology, writing—original draft, and writing—review and editing.
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Rageh, A.H., Said, M.I. & Abdel-aal, F.A.M. Zirconium-based hydrophobic-MOFs as innovative electrode modifiers for flibanserin determination: Exploring the electrooxidation mechanism using a comprehensive spectroelectrochemical study. Microchim Acta 191, 236 (2024). https://doi.org/10.1007/s00604-024-06297-1
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DOI: https://doi.org/10.1007/s00604-024-06297-1