Facile Electrochemical Determination of Methotrexate (MTX) Using Glassy Carbon Electrode-Modified with Electronically Disordered NiO Nanostructures.

Aftab A Khand,Mohd Ubaidullah,Asma A Alothman,Saeed A Lakho,Aneela Tahira,Zafar H Ibupoto,Khoulwod Aljadoa,Ayman Nafady

doi:10.3390/nano11051266

Aftab A Khand, Mohd Ubaidullah + Show 6 more

Open Access

https://doi.org/10.3390/nano11051266

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Abstract

Recently, the oxidative behavior of methotrexate (MTX) anticancer drug is highly demanded, due to its side effects on healthy cells, despite being a very challenging task. In this study, we have prepared porous NiO material using sodium sulfate as an electronic disorder reagent by hydrothermal method and found it highly sensitive and selective for the oxidation of MTX. The synthesized NiO nanostructures were characterized by scanning electron microscope (SEM) and X-ray diffraction (XRD) techniques. These physical characterizations delineated the porous morphology and cubic crystalline phase of NiO. Different electrochemical approaches have been utilized to determine the MTX concentrations in 0.04 M Britton–Robinson buffer (BRB) at pH 2 using glassy carbon electrode (GCE)-modified with electronically disordered NiO nanostructures. The linear range for MTX using cyclic voltammetry (CV) was found to be from 5 to 30 nM, and the limit of detection (LOD) and limit of quantification (LOQ) were 1.46 nM and 4.86 nM, respectively, whereas the linear range obtained via linear sweep voltammetry (LSV) was estimated as 15–90 nM with LOD and LOQ of 0.819 nM and 2.713 nM, respectively. Additionally, amperometric studies revealed a linear range from 10 to70 nM with LOD and LOQ of 0.1 nM and 1.3 nM, respectively. Importantly, MTX was successfully monitored in pharmaceutical products using the standard recovery method. Thus, the proposed approach for the synthesis of active metal oxide materials could be sued for the determination of other anticancer drugs in real samples and other biomedical applications.

Highlights

NiO nanostructures were obtained through the hydrothermal method, and the used methodology is described as follows: The nickel chloride hexahydrate of 0.1 M concentration was mixed with 0.1 M urea in two separate beakers, and an amount of 50 and 100 mg of sodium sulfate as electronic disorder reagent was added
From the top surface analysis, it is clear that using a sodium sulfate could enlarge the structure with a more defined morphology, which has shown a great impact on the functional properties of NiO
Sample 1 and sample 2 were studied by X-ray diffraction (XRD), as shown in Figure 1B(b,c), and the measured reflections confirm the cubic phase of NiO

Summary

Introduction

For measurement of MTX from blood samples, HPLC is the most reliable and predominantly used technique [15–19] These methods are restricted due to their high cost and complexity of the operation. Electroanalytical methods are low cost, simple, selective, sensitive, very fast in response, and easy-to-handle, on-spot measurements. These methods require highly active electrocatalytic materials that can measure MTX selectively under in vitro and real sample conditions. Nanostructured materials offer a high surface area for the sensing applications; different morphologies at the nano level have shown outperforming properties in sensing electronics and optoelectronics applications [44–46]. 0.1 nM, and 1.3 nM, respectively, using the LSV mode of analysis

Chemical and Reagent

Synthesis of NiO Nanostructures

Electrochemical Sensing of MTX Anticancer Drug Using NiO Nanostructures

Morphology and Crystallography Studies of Prepared NiO Nanostructures

Electrochemical

Conclusions