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Article

Determination of Methotrexate Using an Electrochemical Sensor Based on Carbon Paste Electrode Modified with NiO Nanosheets and Ionic Liquid

by
Peyman Mohammadzadeh Jahani
1,
Somayeh Tajik
2,
Hadi Beitollahi
3,*,
Fariba Garkani Nejad
3 and
Zahra Dourandish
3,*
1
School of Medicine, Bam University of Medical Sciences, Bam P.O. Box 76617-71967, Iran
2
Research Center of Tropical and Infectious Diseases, Kerman University of Medical Sciences, Kerman P.O. Box 76169-13555, Iran
3
Environment Department, Institute of Science and High Technology and Environmental Sciences, Graduate University of Advanced Technology, Kerman P.O. Box 76318-85356, Iran
*
Authors to whom correspondence should be addressed.
Chemosensors 2024, 12(12), 266; https://doi.org/10.3390/chemosensors12120266
Submission received: 4 November 2024 / Revised: 6 December 2024 / Accepted: 9 December 2024 / Published: 17 December 2024
(This article belongs to the Special Issue Progress of Photoelectrochemical Analysis and Sensors)
Browse Figures
Figure 1
<p>XRD pattern of NiO NSs.</p> "> Figure 2
<p>FE-SEM images of NiO NSs at three different magnifications (scale bars: 1 µm (<b>a</b>), 500 nm (<b>b</b>), and 200 nm (<b>c</b>)).</p> "> Figure 3
<p>CVs of bare CPE (curve a), NiO NSs/CPE (curve b), and NiO NSs/IL/CPE (curve c) in 0.1 M phosphate buffer solution (pH 7.0) containing 50.0 µM MTX (scan rate: 50 mV/s).</p> "> Figure 4
<p>LSVs of the modified CPE with NiO NSs/IL in 0.1 M phosphate buffer solution (pH 7.0) at different scan rates: 10 mV s<sup>−1</sup> (1), 20 mV s<sup>−1</sup> (2), 40 mV s<sup>−1</sup> (3), 60 mV s<sup>−1</sup> (4), 80 mV s<sup>−1</sup> (5), 100 mV s<sup>−1</sup> (6), 200 mV s<sup>−1</sup> (7), 300 mV s<sup>−1</sup> (8), and 400 mV s<sup>−1</sup> (9). The plot of the peak current vs. Ʋ<sup>1</sup>/<sup>2</sup> (Inset) from 10 mV s<sup>−1</sup> to 400 mV s<sup>−1</sup> containing 50.0 µM MTX.</p> "> Figure 5
<p>Linear sweep voltammogram of the modified CPE with NiO NSs/IL in 0.1 M phosphate buffer solution (pH 7.0) at scan rate 10 mV s<sup>−1</sup>. Inset: Tafel plot (50.0 μM MTX) derived from the rising portion of the voltammogram recorded.</p> "> Figure 6
<p>Chronoamperograms of 0.1 mM (1), 0.7 mM (2), 1.2 mM (3), 2.2 mM (4), and 3.0 mM (5) of MTX at the NiO NSs/IL/CPE sensor. (Inset <b>A</b>): variations of I<sub>p</sub> vs. t<sup>−1/2</sup> taken from chronoamperograms and (Inset <b>B</b>): plot of corresponding slopes against MTX concentration (0.1–3.0 mM).</p> "> Figure 7
<p>DPVs of NiO NSs/IL/CPE in phosphate buffer solution (0.1 M pH 7.0) in the presence of different concentrations of MTX: 0.01 µM (1), 0.1 µM (2), 0.5 µM (3), 1.0 µM (4), 5.0 µM (5), 10.0 µM (6), 20.0 µM (7), 40.0 µM (8), 60.0 µM (9), 80.0 µM (10), 100.0 µM (11), 120.0 µM (12), 140.0 µM (13), and 160.0 µM (14). DPVs were recorded at the following conditions: step potential of 0.01 V, scan rate of 50 mV/s, and pulse amplitude of 0.025 V. The plot of the I<sub>p</sub> vs. various concentrations of MTX (Inset) from 0.01 µM to 160.0 µM.</p> ">
Versions Notes

Abstract

:
In this paper, the application of NiO nanosheets (NiO NSs) for the detection of methotrexate (MTX) is described. The NiO NSs were synthesized using a hydrothermal method. The electrocatalytic activity of two modifiers, ionic liquid (IL) and NiO NSs, was examined on a carbon paste electrode (CPE) in relation to MTX, utilizing voltammetry methods such as cyclic voltammetry (CV), linear sweep voltammetry (LSV), differential pulse voltammetry (DPV), and chronoamperometry at 0.1 M phosphate buffer solution (PBS) pH = 7.0. The anodic peak currents for MTX on the NiO NSs/IL/CPE were approximately 3.5 times greater than those on unmodified CPE. Based on DPV measurements, the electrochemical sensor demonstrated a linear response in the concentration range (LDR: 0.01 µM to 160.0 µM), with a limit of detection (LOD: 0.003 µM). Moreover, the NiO NSs/IL/CPE sensor demonstrated good stability, repeatability, reproducibility, and selectivity, which were of importance in the electroanalysis of compounds. Lastly, the practicality of the NiO NSs/IL/CPE sensor was assessed by analyzing MTX levels in urine samples and pharmaceutical formulation, yielding satisfactory recovery rates of 97.1% to 103.3%.

1. Introduction

Drug development involves multiple stages, including formulation, pharmacodynamics, stability studies, quality control, pharmacokinetics, and both preclinical and clinical testing, all of which necessitate quantitative drug analysis. Accurate methods are essential for assessing drugs in their pure forms, intermediates, and formulations. Given the rising prevalence of diseases like cancer and viral infections, monitoring the medications in use is increasingly important. Cancer is among the leading causes of death on a global scale. The high incidence of cancer has resulted in a greater reliance on chemotherapeutic agents, as chemotherapy remains one of the most common treatment options. Methotrexate (MTX) is one such chemotherapeutic agent, recognized as a folate antagonist that inhibits dihydrofolate reductase, thereby reducing DNA synthesis and limiting cell mitosis and proliferation. It is widely used to treat conditions such as acute lymphoblastic leukemia, breast carcinoma, and various malignant tumors, as well as autoimmune disorders like rheumatoid arthritis and lupus [1,2]. However, MTX, as a cytotoxic agent, affects not only cancerous cells but also healthy cells and tissues, leading to side effects such as liver fibrosis, bone marrow suppression, and potentially severe complications like pneumonitis and baldness [3]. Therefore, precise measurement of MTX levels is essential for providing healthcare professionals with critical clinical insights [4,5,6]. High-dose MTX treatment can lead to significant adverse effects, making it crucial to monitor concentrations of the drug for administration. However, existing methods (such as liquid chromatography-tandem mass spectrometry (LC-MS/MS), ultraperformance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS), high performance liquid chromatography (HPLC), and fluorescent) tend to be complex, time-consuming, and costly. There is an increasing need for a convenient and rapid detection method for MTX [7,8,9,10]. Among various analytical techniques, electrochemical methods are particularly promising. Advances in electrode fabrication and the use of diverse functional materials have significantly enhanced the development of electrochemical sensors for analyte detection. By contrast, electrochemical sensors modified or fabricated through a cost-effective process can offer fast and continuous detection of MTX in real samples with high sensitivities and robustness [11,12,13,14,15,16,17,18,19,20,21,22,23].
Electroanalytical methods provide numerous advantages over conventional analytical techniques, including shorter analysis times, lower detection limits, and improved sensitivity, especially when using modified electrodes [24]. Furthermore, these methods are relatively cost-effective and involve straightforward procedures. Electrochemical analysis has been employed to quickly assess a wide range of pharmaceuticals. Carbon-based electrodes are commonly used in electroanalytical applications due to their high sensitivity, broad potential range, and low background current. To improve detection performance, developing a modified electrochemical sensor is essential. Carbon-based electrodes, including glassy carbon electrodes (GCEs), carbon paste electrodes (CPEs), and screen-printed carbon electrodes (SPCEs) are popular choices for electrochemical sensors because of their versatility and wide range of applications [25,26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43].
Ionic liquids (ILs) are noteworthy due to their distinctive physical and chemical properties. These characteristics include high thermal stability, negligible vapor pressure, low melting points, excellent electrochemical stability, and low toxicity. In this regard, ILs offer numerous efficient applications, from green solvents to electrochemical devices. ILs have a variety of applications in electrochemical sensors. In particular, ILs have been used as a special class of modifying agents for CPEs due to their unique properties [44,45,46,47,48]. The typical features observed upon incorporating ILs into CPEs encompass good stability, high conductivity, effective catalytic properties, improved sensitivity, and enhanced linearity.
Nanotechnology has sparked a significant revolution in the field of materials, particularly in the development of nanostructured materials. Nanotechnology, as a comprehensive and innovative field, provides numerous possibilities for improving processes and products in different fields, from advanced industries to health, energy, and the environment. Also, these materials enhance the electrochemical performance of sensors due to their increased surface area. Various nanostructured materials with morphologies such as nanorods, nanosheets, nanobelts, nanoflakes, and nanocolumns, have been utilized in sensors. Designing a nanostructure with the desired morphology and size can be an effective strategy. Owing to their strong electrocatalytic activity, fast electron transport, reduced dimension, low price, high degree of crystalline nature, and large surface-to-volume ratio, metal oxide nanomaterials have been extensively employed and are already established as an active electrocatalyst. Metal oxide nanoparticles possess unique electrical and structural properties, making them highly adaptable across multiple fields, including water purification, electrochemical sensors, and biosensors. Among these, nickel oxide (NiO) is recognized as an excellent material for electrochemical applications [49,50,51,52,53,54].
In this study, we developed an ultrasensitive electrochemical sensor (NiO NSs/IL/CPE) for MTX detection, utilizing NiO NSs and IL (1-butyl-3-methylimidazolum hexafluorophosphate). The NiO NSs were synthesized via a hydrothermal method. Sensitive voltammetric detection of MTX was carried out by using NiO NSs/IL/CPE sensor. For MTX determination, the designed sensor showed a suitable analytical performance with a wide linear range and low limit of detection (LOD). Also, the NiO NSs/IL/CPE sensor demonstrated exceptional performance in detecting MTX, showcasing excellent stability, repeatability, selectivity, and reproducibility. Additionally, the sensor was successfully employed for the detection of MTX in real samples.

2. Experimental Section

2.1. Materials and Apparatus

All chemicals, including methotrexate (MTX), Ni(NO3)2·6H2O, urea, trisodium citrate dihydrate, ethanol, H3PO4, NaOH, and etc., were of analytical reagent grade from Sigma-Aldrich and Merck (Darmstadt, Germany).
Chronoamperometry, linear sweep voltammetry (LSV), cyclic voltammetry (CV), and differential pulse voltammetry (DPV) were conducted using an Autolab PGSTAT 302N electroanalytical system (Metrohm, Herisau, Switzerland)), which connected to a three-electrode cell. The set of three electrodes included a reference electrode “Ag/AgCl/KCl saturated (Urmia, Iran)”, an auxiliary electrode (Urmia, Iran) “platinum wire”, and a working electrode “NiO NSs/IL/CPE”.

2.2. Synthesis of NiO NSs

The NiO NSs were synthesized using a simple hydrothermal approach according to the previously reported procedure by Wang et al. [55] with slight modifications. Firstly, a solution containing 0.0421 g of Ni(NO3)2·6H2O, 0.1681 g of urea and 0.0058 g of trisodium citrate dihydrate was prepared through dissolving these procedures into 70 mL of deionized water. The dissolution process was performed under magnetic stirring for 45 min at an ambient temperature to ensure complete dissolution of the obtained solution. Then, the hydrothermal reaction of this solution was performed into an autoclave at 150 °C for 24 h. After 24 h, the autoclave was cooled at ambient temperature conditions. After that, the prepared precipitate was collected by centrifugation and washed several times with ethanol/deionized water before being dried at 72 °C for 15 h. Finally, the as-prepared NiO NSs were calcined at 300 °C for 2 h.

2.3. Fabrication of NiO NSs/IL/CPE

A total of 4.0 mg of NiO NSs was mixed with 196.0 mg of graphite powder using a mortar and pestle. A syringe was used to add paraffin oil (60 µL) and IL (20 µL) to the mixture, which was thoroughly mixed for 40 min to wet the paste uniformly. This paste was then packed in a glass tube and the electrical contact was established by placing a copper wire behind the mixture. Excess paste was pushed out of the tube and polished on the paper to reveal a fresh surface if needed. For unmodified CPE and NiO NSs modified CPE the same procedure was followed.

3. Results and Discussion

3.1. Characterization of NiO NSs

The crystalline structure of the NiO NSs was identified by X-ray diffraction (XRD). Figure 1 exhibits the XRD pattern of NiO NSs. The observed peaks at 2θ = 37.1°, 43.1°, 62.6°, 75.1°, and 79.3° can be assigned to the diffraction from (111), (200), (220), (311), and (222) planes of NiO, respectively. Additionally, the recorded XRD pattern confirmed the formation of NiO with a cubic structure (JCPDS: 78-0643) which was in good agreement with reported XRD patterns in the literature [56,57,58].
To investigate the morphological features of the NiO NSs, the characterization was carried out by using a field emission scanning electron microscope. The field emission scanning electron microscopy (FE-SEM) images of NiO NSs are shown in Figure 2. The FE-SEM images revealed that the as-synthesized NiO is composed of two-dimensional (2D) NSs. Also, the NiO NSs have a thickness of about 15 nm. Also, by assembling these NSs, microspheres were formed.

3.2. Electroactive Surface Area

The electroactive surface area of electrodes is an important parameter, because it can significantly affect the ability of an electrochemical sensor for determination of various compounds. In order to calculate the electroactive surface areas of bare CPE and NiO NSs/IL/CPE, a study of CV at various scan rates was carried out. The cyclic voltammograms were recorded for 5.0 mM ([Fe(CN)6]3−/4−) as a redox couple in 0.1 M KCl on the bare CPE and NiO NSs/IL/CPE at different scan rates (10 mV/s, 25 mV/s, 50 mV/s, 75 mV/s, 100 mV/s, 250 mV/s, and 500 mV/s). The calculations for electroactive surface areas of these electrodes were conducted by using the slopes of the corresponding plots (anodic peak currents versus the square root of scan rate (υ1/2) plots) and the Randles–Sevcik equation [59]:
Ipa = 2.69 × 105n3/2ACD1/2ʋ1/2
where n is the number of electrons transferred in the oxidation-reduction process (redox process) of the redox couple, A is the electroactive surface area of the working electrode (WE)—cm2, C is the concentration of the electroactive species in solution (redox couple)—mol/cm3, D is the diffusion coefficient of the redox couple—cm2/s, and υ is the scan rate—mV/s. Based on the obtained results, the electroactive surface areas of bare CPE and NiO NSs/IL/CPE were found to be 0.12 cm2 and 0.38 cm2, respectively. Therefore, the surface area of NiO NSs/IL/CPE was significantly higher than bare CPE.

3.3. Electrochemical Behavior of MTX

The CV technique was used to investigate the electrocatalytic activities of unmodified CPE, NiO NSs-modified CPE, and NiO NSs/IL-modified CPE for electrochemical reactions of MTX. From Figure 3, MTX oxidation in bare CPE shows a weak oxidation signal (5.6 μA) at high oxidation potential (780 mV) (CV a). The NiO NSs-modified CPE (CV b) showed a higher oxidation signal (9.7 µA) compared to bare CPE, demonstrating the efficient role of NiO NSs in the oxidation of MTX. After CPE modification with NiO NSs/IL, the MTX oxidation signal shifted to 570 mV and the oxidation current significantly increased to 20.0 µA (CV c) compared to bare CPE and NiO NSs/CPE. This indicates a significant decrease in potential and increase in current than other electrodes. The significant increase in oxidation peak current and decrease in the oxidation peak potential could be related to the good electrocatalytic activity of NiO NSs/IL-modified CPE from high conductivity of IL and high electroactive surface area of NiO NSs. Consequently, NiO NSs/IL/CPE was used for electrochemical measurements of MTX.

3.4. Effect of Scan Rate

The effects of scan rate were examined, and the results are presented in Figure 4. In this study, several LSVs were recorded at varying scan rates from 10 to 400 mV/s using a 50.0 µM MTX solution. As shown in Figure 4 (Inset), there is a strong linear relationship (R2 = 0.9982) between the anodic peak current (Ip) and the square root of the scan rate (Ʋ1/2), indicating that the electro-oxidation of MTX at the surface of the NiO NSs/IL/CPE is a diffusion-controlled process.

3.5. Tafel Plot

Figure 5 (inset) shows a Tafel plot obtained from the rising portion of the current–voltage curve at a scan rate of 10 mV/s for 50.0 μM MTX. The kinetics of the electrode process is represented by a linear relationship between E and log I. The estimated Tafel slope is shown in Figure 5 (Inset) as 0.1117 V, suggesting that the rate-limiting step involves a one-electron transfer process, with a transfer coefficient (α) of 0.47.

3.6. Chronoamperometry

To determine the diffusion coefficient of MTX, chronoamperometry was performed using the NiO NSs/IL/CPE with varying concentrations of MTX. Figure 6 displays the current–time curves obtained by setting the electrode potential at 620 mV for different MTX concentrations. A plot of current (I) versus the reciprocal of the square root of time (t−1/2) for these concentrations produced straight lines (Figure 6A) with varying slopes. Then, the slopes of these straight lines were drawn against the corresponding concentrations of MTX (Figure 6B). The resulting slope of this plot can be used to estimate the diffusion coefficient (D) of MTX based on the Cottrell equation. The average diffusion coefficient (D) for MTX was determined to be 1.15 × 10−5 cm2/s.

3.7. Determination of MTX by Using the DPV Method

The relationship between Ip and concentration is a crucial method for the quantitative estimation of analytes and for calculating the LOD. Therefore, DPV was utilized to determine MTX at the NiO NSs/IL/CPE. As shown in Figure 7, a strong linear correlation between peak current (Ip) and MTX concentration was observed in the range of 0.01 µM to 160.0 µM. The LOD for MTX at the NiO NSs/IL/CPE was found to be 0.003 µM. The LOD was calculated by using LOD = 3Sb/m (Sb: standard deviation of the 12 measurements of blank solution, and m: slope of the calibration plot). The obtained values for LOD and the linear range of MTX are compared with the values reported within the literature (Table 1). According to the summarized data in Table 1, the designed sensor in this work (NiO NSs/IL/CPE) demonstrated wider linear range in comparison to most of the reported electrochemical sensors based on modified electrodes in the literature for MTX determination. Also, the value of LOD obtained with the NiO NSs/IL/CPE sensor was lower in comparison to most of the reported sensors. This comparison reveals that the NiO NSs/IL-modified CPE has good performance in electrochemical sensing platforms to determine MTX.

3.8. Stability, Repeatability, and Reproducibility of the Designed Sensor for MTX Determination

Examining stability, repeatability, and reproducibility parameters is crucial for evaluating the performance of an electrochemical sensor because they directly impact the reliability and accuracy of its measurements over time and under varying conditions. The long-term stability of the NiO NSs/IL/CPE sensor was investigated by monitoring the current response to MTX (50.0 µM) over four weeks (measurements taken every four days). The results indicated a slight decrease in the response peak current. The response peak current towards MTX remained 94.5% of its initial value after four weeks. Also, the repeatability of the NiO NSs/IL/CPE sensor was assessed by running ten successive DPV measurements of 50.0 µM MTX. The DPV measurements provided good repeatability with a relative standard deviation (RSD) of 3.5%. Additionally, to assess the reproducibility of the NiO NSs/IL/CPE sensor, eight identical sensors were utilized to measure 50.0 μM MTX using DPV. The RSD of the peak current response was found to be 3.6%. These findings confirm that the NiO NSs/IL/CPE exhibits good reproducibility, repeatability, and storage stability.

3.9. Interference Studies

Real samples contain various species that can influence the detection and sensitivity capabilities of electrodes. To study the interference effects of these species, we observed changes in the oxidation peak current of MTX. Consequently, the anti-interference ability of the modified electrode is a critical factor affecting monitoring accuracy. This study shows that the presence of various interferences, at concentrations up to several times greater than that of MTX, does not significantly impact the sensitivity and detection capabilities of the NiO NSs/IL modified CPE. For example, in the detection of MTX using NiO NSs/IL/CPE, a 500-fold concentration of Mg2+, NH4+, Ca2+, and Fe3+ resulted in slight changes in the peak current (less than 5%). Similarly, when employing the same electrode for MTX detection, a 20-fold concentration of tartaric acid, dopamine, glucose, vitamin C, vitamin B6, and sucrose led to signal changes below 5%. Additionally, the effect of doxorubicin in the determination of MTX (at equal concentrations) has been investigated. It was observed that the current signal in the response to MTX had decreased slightly (4.7%). Table 2 shows the effect of some possible interfering compounds on the signal change of MTX (20.0 µM).

3.10. Measurement of MTX in Real Samples

The proposed sensor was successfully utilized for both pharmaceutical formulations and urine samples. The effectiveness of the NiO NSs/IL/CPE for electrochemical detection of MTX in the real samples was assessed using DPV. Firstly, the prepared solutions of MTX tablet and urine samples were separately added to the electrochemical cell and were analyzed. Then, standard solutions of MTX at known concentrations were added into the real samples and the corresponding DPVs obtained for each addition were recorded. The concentrations of MTX in these samples were found using the DPV method by the standard addition method for five replicate measurements. The results from this investigation are summarized in Table 3. Recovery percentages ranged from 97.1% to 103.3%, with RSDs of less than 3.6%. These findings indicate that the NiO NSs/IL/CPE is a suitable platform for the efficient determination of MTX in real samples. Also, these findings show that the developed method possesses adequate accuracy and precision to determine MTX in the practical analyses.

4. Conclusions

In conclusion, NiO NSs/IL-modified CPE was created for the voltammetric detection of MTX. NiO NSs were successfully synthesized and characterized using FE-SEM and XRD. From CV studies, it was found that the NiO NSs/IL-modified CPE significantly enhanced the current and reduced the overvoltage in the oxidation process of MTX. Under optimized conditions, the oxidation peak current exhibited a linear relationship with MTX concentration, ranging from 0.01 µM to 160 µM, and the correlation coefficient was 0.9998, with a LOD of 0.003 µM (3Sb/m). Also, the NiO NSs/IL/CPE sensor demonstrated good selectivity towards MTX in the presence of some possible interfering compounds in addition to its good storage stability, reproducibility, and repeatability. The proposed sensor was successfully used for the determination of MTX in real samples, with recovery rates of between 97.1% and 103.3%. This approach may provide opportunities for the MTX determination in practical applications.

Author Contributions

Formal analysis, P.M.J., S.T., H.B., F.G.N. and Z.D.; Writing—original draft, P.M.J., S.T., H.B., F.G.N. and Z.D.; Writing—review & editing, P.M.J., S.T., H.B., F.G.N. and Z.D. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

The data presented in this study are available on request from the corresponding authors.

Conflicts of Interest

The authors have no declaration of interest.

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Chemosensors 12 00266 g001
Figure 1. XRD pattern of NiO NSs.
Figure 1. XRD pattern of NiO NSs.
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Figure 2. FE-SEM images of NiO NSs at three different magnifications (scale bars: 1 µm (a), 500 nm (b), and 200 nm (c)).
Figure 2. FE-SEM images of NiO NSs at three different magnifications (scale bars: 1 µm (a), 500 nm (b), and 200 nm (c)).
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Figure 3. CVs of bare CPE (curve a), NiO NSs/CPE (curve b), and NiO NSs/IL/CPE (curve c) in 0.1 M phosphate buffer solution (pH 7.0) containing 50.0 µM MTX (scan rate: 50 mV/s).
Figure 3. CVs of bare CPE (curve a), NiO NSs/CPE (curve b), and NiO NSs/IL/CPE (curve c) in 0.1 M phosphate buffer solution (pH 7.0) containing 50.0 µM MTX (scan rate: 50 mV/s).
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Figure 4. LSVs of the modified CPE with NiO NSs/IL in 0.1 M phosphate buffer solution (pH 7.0) at different scan rates: 10 mV s−1 (1), 20 mV s−1 (2), 40 mV s−1 (3), 60 mV s−1 (4), 80 mV s−1 (5), 100 mV s−1 (6), 200 mV s−1 (7), 300 mV s−1 (8), and 400 mV s−1 (9). The plot of the peak current vs. Ʋ1/2 (Inset) from 10 mV s−1 to 400 mV s−1 containing 50.0 µM MTX.
Figure 4. LSVs of the modified CPE with NiO NSs/IL in 0.1 M phosphate buffer solution (pH 7.0) at different scan rates: 10 mV s−1 (1), 20 mV s−1 (2), 40 mV s−1 (3), 60 mV s−1 (4), 80 mV s−1 (5), 100 mV s−1 (6), 200 mV s−1 (7), 300 mV s−1 (8), and 400 mV s−1 (9). The plot of the peak current vs. Ʋ1/2 (Inset) from 10 mV s−1 to 400 mV s−1 containing 50.0 µM MTX.
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Figure 5. Linear sweep voltammogram of the modified CPE with NiO NSs/IL in 0.1 M phosphate buffer solution (pH 7.0) at scan rate 10 mV s−1. Inset: Tafel plot (50.0 μM MTX) derived from the rising portion of the voltammogram recorded.
Figure 5. Linear sweep voltammogram of the modified CPE with NiO NSs/IL in 0.1 M phosphate buffer solution (pH 7.0) at scan rate 10 mV s−1. Inset: Tafel plot (50.0 μM MTX) derived from the rising portion of the voltammogram recorded.
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Figure 6. Chronoamperograms of 0.1 mM (1), 0.7 mM (2), 1.2 mM (3), 2.2 mM (4), and 3.0 mM (5) of MTX at the NiO NSs/IL/CPE sensor. (Inset A): variations of Ip vs. t−1/2 taken from chronoamperograms and (Inset B): plot of corresponding slopes against MTX concentration (0.1–3.0 mM).
Figure 6. Chronoamperograms of 0.1 mM (1), 0.7 mM (2), 1.2 mM (3), 2.2 mM (4), and 3.0 mM (5) of MTX at the NiO NSs/IL/CPE sensor. (Inset A): variations of Ip vs. t−1/2 taken from chronoamperograms and (Inset B): plot of corresponding slopes against MTX concentration (0.1–3.0 mM).
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Figure 7. DPVs of NiO NSs/IL/CPE in phosphate buffer solution (0.1 M pH 7.0) in the presence of different concentrations of MTX: 0.01 µM (1), 0.1 µM (2), 0.5 µM (3), 1.0 µM (4), 5.0 µM (5), 10.0 µM (6), 20.0 µM (7), 40.0 µM (8), 60.0 µM (9), 80.0 µM (10), 100.0 µM (11), 120.0 µM (12), 140.0 µM (13), and 160.0 µM (14). DPVs were recorded at the following conditions: step potential of 0.01 V, scan rate of 50 mV/s, and pulse amplitude of 0.025 V. The plot of the Ip vs. various concentrations of MTX (Inset) from 0.01 µM to 160.0 µM.
Figure 7. DPVs of NiO NSs/IL/CPE in phosphate buffer solution (0.1 M pH 7.0) in the presence of different concentrations of MTX: 0.01 µM (1), 0.1 µM (2), 0.5 µM (3), 1.0 µM (4), 5.0 µM (5), 10.0 µM (6), 20.0 µM (7), 40.0 µM (8), 60.0 µM (9), 80.0 µM (10), 100.0 µM (11), 120.0 µM (12), 140.0 µM (13), and 160.0 µM (14). DPVs were recorded at the following conditions: step potential of 0.01 V, scan rate of 50 mV/s, and pulse amplitude of 0.025 V. The plot of the Ip vs. various concentrations of MTX (Inset) from 0.01 µM to 160.0 µM.
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Table 1. Comparison of the present work with other reported works for determination of MTX.
Table 1. Comparison of the present work with other reported works for determination of MTX.
Electrochemical Sensors Based on Modified ElectrodesElectrochemical MethodLDRLODRef.
a UiO-66-NH2 MOF/M-gC3N4/Au NPs-modified CPEDPV0.5 µM to 150 µM0.15 µM[11]
b GQDs/Au NPs/ANSA-modified GCEDPV0.1 µM to 100 µM 0.03 µM[12]
c NbO/NbC/rGO-modified GCEDPV0.1 µM to 850 µM1.6 nM[13]
d V2O5@g-C3N4 nanocomposite-modified SPCEDPV0.025 µM to 273.15 µM13.26 nM[14]
e CoFe2O4 NPs/IL-rGO-modified GCEDPV0.05 µM to 7.5 µM10 nM[15]
f BP-3DGr@BCu NPS-modified GCESquare wave voltammetry (SWV)0.5 µM to 210.0 µM0.36 nM[16]
g Poly (L-Cys)/g-C3N4-modified GCE DPV7.5 µM to 78.0 µM6 nM[17]
h GO-nafion-modified GCECV0.4 µM to 15 µM0.009 µM[18]
i CNOs/Fe3O4 NPs@NH2-MCM-41 NPs-modified GCEDPV0.01 µM to 50 µM3 nM[19]
j MOF-derived NiO/Ni@C-PINA-modified GCEDPV0.02 µM to 2.5 µM7.2 nM[20]
k Antimony oxide@bismuth oxide nanocomposite-modified GCEChronoamperometry0.01 µM to 174.6 µM2.9 nM[21]
l PANI-assisted Co3O4 NPs-modified GCECV5 µM to 75 µM1.98 µM[22]
m 3D Gr-CNTs-modified GCEDPV0.7 µM to 100 µM70 nM[23]
n CFL-Ho3+/NiO NSs-modified GCEDPV0.001 µM to 310.0 µM5.2 nM[60]
NiO NSs/IL/CPEDPV0.01 µM to 160 µM0.003 µMThis work
a: UiO-66-NH2 metal-organic framework/mesoporous carbon nitride/Au nanoparticles-modified carbon paste electrode; b: Graphene quantum dots/Au nanoparticles/1-amino-2-naphtol-4-sulfonic acid-modified glassy carbon electrode; c: Niobium oxide/niobium carbide/reduced graphene oxide ternary nanocomposite-modified glassy carbon electrode; d: V2O5@g-C3N4 nanocomposite-modified screen-printed carbon electrode; e: CoFe2O4 nanoparticles/ionic liquid-reduced graphene oxide-modified glassy carbon electrode; f: Structure of multi-layered petal-shaped black phosphorous-three dimensional graphene@bio synthesized Cu NPs-modified glassy carbon electrode; g: Poly (L-Cysteine)/graphitic carbon nitride-modified glassy carbon electrode; h: Graphene oxide-nafion-modified glassy carbon electrode; i: Carbon nano onions/Fe3O4 nanoparticles@aminated MCM-41 nanoparticles-modified glassy carbon electrode; j: Metal-organic framework-derived NiO/Ni@C-poly(isonicotinic acid)-modified glassy carbon electrode; k: Sb2O3@Bi2O3 nanocomposite-modified glassy carbon electrode; l: Polyaniline-assisted Co3O4 nanoparticles-modified glassy carbon electrode; m: Three dimensional graphene-carbon nanotubes-modified glassy carbon electrode; n: Cabbage flower-like Ho3+/NiO nanostructures-modified glassy carbon electrode.
Table 2. The effect of some possible interfering compounds in determination of 20.0 µM MTX in phosphate buffer solution (0.1 M with pH 7.0).
Table 2. The effect of some possible interfering compounds in determination of 20.0 µM MTX in phosphate buffer solution (0.1 M with pH 7.0).
Interfering CompoundsCInterfering compound/CMTXSignal Change (%)
Mg2+500-fold3.6
NH4+500-fold2.9
Ca2+500-fold3.4
Fe3+500-fold2.5
tartaric acid20-fold2.8
dopamine20-fold4.0
glucose20-fold3.7
vitamin C20-fold4.1
vitamin B620-fold3.9
sucrose20-fold3.5
doxorubicinequal4.7
Table 3. Determination of MTX on the NiO NSs/IL/CPE surface in real samples (n = 5).
Table 3. Determination of MTX on the NiO NSs/IL/CPE surface in real samples (n = 5).
SampleSpiked Concentration Found Concentration RecoveryRSD
MTX tablet0 µM2.9 µM-3.3%
2.0 µM5.0 µM102.0%2.8%
3.0 µM5.8 µM98.3%1.9%
4.0 µM6.7 µM97.1%2.7%
5.0 µM8.1 µM102.5%2.9%
urine0 µM---
5.0 µM4.9 µM98.0%1.8%
6.0 µM6.2 µM103.3%3.6%
7.0 µM6.8 µM97.1%2.2%
8.0 µM8.1 µM101.2%2.6%
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Mohammadzadeh Jahani, P.; Tajik, S.; Beitollahi, H.; Garkani Nejad, F.; Dourandish, Z. Determination of Methotrexate Using an Electrochemical Sensor Based on Carbon Paste Electrode Modified with NiO Nanosheets and Ionic Liquid. Chemosensors 2024, 12, 266. https://doi.org/10.3390/chemosensors12120266

AMA Style

Mohammadzadeh Jahani P, Tajik S, Beitollahi H, Garkani Nejad F, Dourandish Z. Determination of Methotrexate Using an Electrochemical Sensor Based on Carbon Paste Electrode Modified with NiO Nanosheets and Ionic Liquid. Chemosensors. 2024; 12(12):266. https://doi.org/10.3390/chemosensors12120266

Chicago/Turabian Style

Mohammadzadeh Jahani, Peyman, Somayeh Tajik, Hadi Beitollahi, Fariba Garkani Nejad, and Zahra Dourandish. 2024. "Determination of Methotrexate Using an Electrochemical Sensor Based on Carbon Paste Electrode Modified with NiO Nanosheets and Ionic Liquid" Chemosensors 12, no. 12: 266. https://doi.org/10.3390/chemosensors12120266

APA Style

Mohammadzadeh Jahani, P., Tajik, S., Beitollahi, H., Garkani Nejad, F., & Dourandish, Z. (2024). Determination of Methotrexate Using an Electrochemical Sensor Based on Carbon Paste Electrode Modified with NiO Nanosheets and Ionic Liquid. Chemosensors, 12(12), 266. https://doi.org/10.3390/chemosensors12120266

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