Detection of Axitinib Using Multiwalled Carbon Nanotube-Fe2O3/Chitosan Nanocomposite-Based Electrochemical Sensor and Modeling with Density Functional Theory

Ahmet Cetinkaya, S. Irem Kaya, Pelin Şenel, Nejla Cini, Esen B. Atici, Sibel A. Ozkan, Mine Yurtsever*, Ayşegül Gölcü*

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4 Atıf (Scopus)

Özet

In this study, axitinib (AXI), a potent and selective inhibitor of vascular endothelial growth factor receptor (VEGFR) tyrosine kinase and used as a second-generation targeted drug, was investigated electrochemically under optimized conditions using multiwalled carbon nanotubes/iron(III) oxide nanoparticle-chitosan nanocomposite (MWCNT/Fe2O3@chitosan NC) modified on the glassy carbon electrode (GCE) surface. Characterization of the modified electrode was performed using scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). The adsorptive stripping differential pulse voltammetric (AdSDPV) technique was used for the sensitive, rapid, and precise detection of AXI. The current peak obtained with the MWCNT/Fe2O3@chitosan NC modified electrode was 23 times higher compared to the bare electrode. The developed modified electrode showed excellent electrocatalytic activity in AXI oxidation. Under optimized conditions, the effect of supporting electrolyte and pH was investigated, and 0.1 M H2SO4 was chosen as the electrolyte with the highest peak current for the target analyte. In the concentration range of MWCNT/Fe2O3@chitosan NC/GCE, 6 × 10-9 and 1 × 10-6 M, the limit of detection (LOD) and limit of quantification (LOQ) values were calculated to be 0.904 and 0.0301 pM, respectively. Tablet and serum samples were used for the applicability of the developed sensor, relative standard deviation (RSD) values for all samples were below 2%, and the recovery results were 99.23 and 101.84%, respectively. The MWCNT/Fe2O3@chitosan NC/GCE designed to determine AXI demonstrated the applicability, selectivity, precision, and accuracy of the sensor. The mechanism of electron transfer from the modified GCE surface to the analyte solution is studied via modeling the modified GCE surface by the density functional theory (DFT) method at B3LYP/6-311+g(d,p) and M062X/6-31g(d,p) levels. We observed that the iron oxide nanoparticles play an important role in channeling electron flow from the analyte solution to the MWCNT-coated GCE electrode surface. Adsorption of the nanocomposite material onto the GCE surface occurs via strong electrostatic interactions, including ionic and hydrogen bond formations. During the adsorption-controlled oxidation process of the axitinib, the electrons are transferred via the highest occupied molecular orbital (HOMO) localized on the iron oxide moiety to the lowest unoccupied molecular orbital (LUMO) of the MWCNT/GCE surface.

Orijinal dilİngilizce
Sayfa (başlangıç-bitiş)34495-34505
Sayfa sayısı11
DergiACS Omega
Hacim7
Basın numarası38
DOI'lar
Yayın durumuYayınlandı - 27 Eyl 2022

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Publisher Copyright:
© 2022 American Chemical Society.

Finansman

A.C thanks the financial support from the Council of Higher Education (YOK) under the special 100/2000 Ph.D. Scholarship Program and the Scientific and Technological Research Council of Turkey (TUBITAK) under the BIDEB/2211-A Ph.D. Scholarship Program.

FinansörlerFinansör numarası
YOK
Türkiye Bilimsel ve Teknolojik Araştırma Kurumu
Yükseköğretim Kurulu

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