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/Fe
2
O
3
@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/Fe
2
O
3
@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 H
2
SO
4
was chosen
as the electrolyte with the highest peak current for the target analyte.
In the concentration range of MWCNT/Fe
2
O
3
@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/Fe
2
O
3
@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.