Talanta 247 (2022) 123593

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Talanta
journal homepage: www.elsevier.com/locate/talanta

Synthesis, characterization and electrochemical sensors application of

Tb2Ti2O7 nanoparticle modified carbon paste electrode for the sensing of
mefenamic acid drug in biological samples and pharmaceutical
industry wastewater
Movlud Valian a, Asma Khoobi b, Masoud Salavati-Niasari a, *
a
Institute of Nano Science and Nano Technology, University of Kashan, Kashan, P.O. Box 87317-51167, I. R., Iran
b
Department of Chemistry, Faculty of Sciences, University of Sistan and Baluchestan, Zahedan, 98135-674, Iran

A R T I C L E I N F O A B S T R A C T

Keywords: Today, in most fields, wide research has been done in the manufacture of biosensors and the detection of various
Pechini modified method types of substances, including drugs. Nevertheless, the analytical detection of drugs from a biological sample by a
Tb2Ti2O7 nanostructures simple and portable method for on-site detection is still important and very challenging. This paper investigates
Anti-inflammatory drug analysis
the electrochemical determination of the mefenamic acid (MEF), with a novel carbon paste electrode modified
Mefenamic acid
with terbium titanate nanostructures (TTN/CPE). The effect of the capping agent on the morphology and size of
terbium titanate synthesized from terbium nitrate in the presence of ethylene glycol (EG) as a stabilization agent
is investigated. The as-produced nanostructures are characterized by X-ray diffraction (XRD), Fourier transforms
infrared (FT-IR) spectroscopy, energy dispersive X-ray microanalysis (EDX), scanning electron microscopy (SEM)
and high-resolution transmission electron microscopy (HR-TEM). Electrochemical studies in optimized condi­
tions indicate MEF has two linear responses in the range of 1.0 × 10− 2–4.0 × 102 μM with a detection limit of 2.4
nM at the surface of TTN/CPE. The suggested sensor reveals good sensitivity, selectivity, stability, and repro­
ducibility and can be utilized for some important biological samples and wastewater with satisfactory results.

Author cont section
Movlud Valian: Formal analysis, Writing - Original Draft, Method­
ology, Investigation, Software, Writing - Original Draft. Asma Khoobi:
Investigation, Methodology, Writing - Review & Editing. Masoud Sal­
avati-Niasari: Conceptualization, Methodology, Supervision, Project
administration, Validation, Data Curation, Writing - Review & Editing,
Writing - Original Draft, Resources, Visualization, Funding acquisition.
1. Introduction
Mefenamic acid (N-(2,3-xylyl)anthranilic acid, MEF), is a nonste­
roidal, analgesic, and anti-inflammatory drug that extensively is utilized
because of its pain relief and analgesic properties. There are almost as
many different types of painkillers as there are different types of pain.
But only non-steroidal anti-inflammatory drugs such as mefenamic acid
can reduce inflammation. Prostaglandins have been shown to be
responsible for stimulating pain-sensitive receptors, and mefenamic acid
indirectly inhibits the synthesis of prostaglandins by acting on cyclo­
oxygenase (COX) pathways and inhibiting inflammatory pathways, and
as a painkiller reduces pain [1]. These features have made MEF be used
for the relief of pain due to conditions such as rheumatoid arthritis,
osteoarthritis, non-articular rheumatism, post-operative and menstrual
period pains, and also other painful arthralgia illnesses [2,3]. However,
the excessive consumption of this drug can have a poisonous metabolite
accumulation effect and may cause heart attack, acute hepatic necrosis,
and an increase in mortality rate [4]. This high-consumption drug
contains diphenylamine contaminants and is present in significant
amounts in effluents and natural waters, which can impair the repro­
ductive capacity and sex hormones of aquatic. Therefore, this drug is one
of the priority pollutants in the European Union and its sensitive
detection is of great importance in biological and environmental sam­
ples [5]. The benefits and risks of MEF have convinced us to detect it in
pharmaceutical and biological specimens. In view of the significance of

* Corresponding author.
E-mail address: salavati@kashanu.ac.ir (M. Salavati-Niasari).

https://doi.org/10.1016/j.talanta.2022.123593
Received 12 August 2021; Received in revised form 10 November 2021; Accepted 25 May 2022
Available online 26 May 2022
0039-9140/© 2022 Elsevier B.V. All rights reserved.
M. Valian et al. Talanta 247 (2022) 123593

Scheme 1. Schematic diagram for the synthesis of Tb2Ti2O7 nanostructures (sample no. 2).

Table 1
Preparation conditions of Tb2Ti2O7 nanostructures.
Sample Calcination Chelating Acid: Figure of FESEM
No. Temperature (◦ C) agent EG Micrographs

1 700 Oxalic acid 1:6 –

2 800 Oxalic acid 1:6 4 (c, d), 5 (c, d)
3 900 Oxalic acid 1:6 –
4 800 Citric acid 1:6 4 (a, b)
5 800 Malonic 1:6 4 (e, f)
acid
6 800 Oxalic acid 1:1 5 (a, b)
7 800 Oxalic acid 1:12 5 (e, f)

MEF and its wide application, measurement of the drug had been made
using various methods. To our knowledge, some analytical techniques
such as high-performance liquid chromatography [6], spectrophotom­
etry [7–9], polarography [10,11], potentiometry [9], fluorimetry [12],
conductometry [13], and voltammetry [14] have been proposed for the
analysis of MEF in pharmaceutical formulations and biological samples.
As you know, these methods, although highly sensitive, have a high cost
and lack sufficient robustness and portability for on-site detection. Also,
in these instruments, due to the time required to determine, sample
preparation, and the use of large amounts of solvents and chemicals
harmful to the environment, there are many limitations and problems
[15]. However, in electrochemical approaches, this method is a safe
method due to the use of fewer modifiers in the working electrode.
Among the electrodes used in the electrochemical approach, CPE has
Fig. 1. FT-IR spectrum of Tb2Ti2O7 nanostructures prepared at 800 ◦ C in the
presence of oxalic acid.
more important than other working electrodes due to the lack of use of
solvents and harmful chemicals, simple electrode preparation,
cost-effectiveness, high variability in the modifier, lower background
current with a potential window in a wider range and the possibility of
changing and renovating the surface [16]. On the other hand, it has
fewer disadvantages than other methods. Electrochemical detection
methods using various materials have been used as electrode modifiers
with the aim of increasing sensitivity and selectivity [17–19].
Electrochemical studies of modified electrodes with metal nano­
particles, because of their importance have been created the focus of

2
M. Valian et al.
Fig. 2. XRD patterns of Tb2Ti2O7 nanostructures prepared in the presence of:
(a) oxalic acid at 700 ◦ C, (b) oxalic acid at 800 ◦ C and (c) oxalic acid at 900 ◦ C.
Fig. 3. EDS patterns of the Tb2Ti2O7 nanostructures prepared in the presence of
oxalic acid at 800 ◦ C.
serious interest for the last decade worldwide [20,21]. Titanate
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Talanta 247 (2022) 123593
pyrochlores (with the general formula A2Ti2O7; A is metal) are a type of
ceramic compound that is generally recognized as functional materials.
These pyrochlore materials have many potential applications, including
high-temperature gas sensors [22–25], photocatalysts [26–29], fast ion
conductors [30], solid oxide fuel cell electrodes [31–33], materials for
resisting radiation damage [34] and hosts for radioactive waste [32].
Among the rare earth elements, terbium (Tb) as heavy metal, a rare and
expensive element, has low to moderate toxicity [35]. However, terbium
titanate (Tb2Ti2O7) due to their specific structural nature, the existence
of metal in a high oxidation state, the magnetic moment at low tem­
peratures [36], and spin liquid behavior as one of the most appealing
pyrochlore-type oxide have been used extensively in magnetic fields
[37,38], water splitting [39] and electrolyte-insulator-semiconductor
pH sensors [40].
Up to now, diverse chemical synthesis routes have been utilized for
the fabrication of Tb2Ti2O7. Nowadays, the features and efficiency of
nanoscale materials are predominantly affected by their high chemical
purity, shape and grain size. Hence, in recent years, the design and
construction of nanoscale materials with controlled size and shape have
been much discussed [41]. Also, the sol-gel (Pechini) method is an
applied chemical method and cost-effective for the preparation of
Tb2Ti2O7 uniform powder and offers an efficient route to improve the
shape and size.
In this paper, the terbium titanate nanostructures are synthesized by
a recovered Pechini approach. The effect of different parameters on
purity rate, shape, and grain size of the samples (Tb2Ti2O7) such as the
effect of calcination temperature, type of organic acid, and role of the
utilized amount of ethylene glycol are investigated to improve the
morphological characteristics. To our knowledge, it is the first time that
an electrochemical sensor based on terbium titanate nanostructures
(TTN) was constructed for the measurement of MEF in real complicated
samples. Also, the electrochemical behavior of the TTN modified carbon
paste electrode was investigated using cyclic voltammetry (CV) and
differential pulse voltammetry (DPV) techniques. The stability and
reproducibility of the nanostructured modified electrode were consid­
ered and it was used for the monitoring of MEF in human blood serum,
tablet, and wastewater examples.
2. Experimental
2.1. Materials and methods
The whole materials employed in the present study were of analyt­
ical grade. The materials containing Ti(OBu)4, Tb(NO3)3⋅5H2O, ethyl­
alcohol, oxalic acid, citric acid, malonic acid, ethylene glycol (EG), MEF,
and others were purchased from Merck. Britton-Robinson buffers (0.2
M) were prepared from 0.2 M of CH3COOH, H3PO4, H3BO3, and a
saturated solution of sodium hydroxide.
2.2. Synthesis of Tb2Ti2O7 nanostructures
Terbium titanate nanostructures were prepared along with a syn­
thetic procedure as are summarized in Scheme 1. These nanostructures
were prepared through a recovered Pechini process. Tetra-n-butyl
orthotitanate (Ti(OBu)4, 98.0 wt%purity), terbium nitrate (Tb
(NO3)3⋅5H2O, 99.0 wt%purity), organic acid (oxalic acid, 99.0 wt%pu­
rity), ethylalcohol (C2H5OH, 99.5 wt%purity), and ethylene glycol
(HOCH2CH2OH, 99.8 wt% purity) were handled as the crude materials
for the modified Pechini method procedure. A stoichiometric amount of
tetra-n-butyl orthotitanate and terbium nitrate with the cationic ratio of
Ti: Tb = 1:1 were separately dissolved in ethylalcohol, namely solution
A and B, respectively. Oxalic acid was then put into solution A, and it
was kept in transparency. While solution B was carefully poured into the
above-mentioned glassy solution and stirred slowly, the tiny precipitates
came out. Subsequently, ethylene glycol as a stabilization agent was
added into the previous solution and then by uniform evaporation of the
M. Valian et al.
Fig. 4. FESEM micrographs of the Tb2Ti2O7 nanostructures at 800 ◦ C for 2 h, in the presence of (a, b) citric acid, (c, d) oxalic acid, (e, f) malonic acid.
above mixture, a uniform gel was obtained. The molar ratio of oxalic
acid: EG was elected to be 1:1, 1:6, and 1:12. The gel dried at 70 ◦ C for
24 h in a vacuum drying oven and then calcined at 700–900 for 2 h.
Table 1 lists the various experimental situations for the preparation of
Tb2Ti2O7 nanostructures.
2.3. Electrochemical cell
Using voltammetry techniques in a three-electrode electrochemical
cell, the electrochemical behavior of the modified electrodes based on
Tb2Ti2O7 nanostructures was measured. The system contains a bare CPE
or CPE modified with Tb2Ti2O7 nanostructures (TTN/CPE), an Ag/AgCl/
KCl (3.0 M) (Metrohm, Switzerland), and a Pt wire (Metrohm,
Switzerland) as the working, reference and counter electrodes, respec­
tively. To prepare TTN/CPE, 0.06 g of Tb2Ti2O7 nanopowder and 5.0 mL
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Talanta 247 (2022) 123593
of deionized water were mixed together. The resulting suspension was
dispersed by ultrasound bath for 30 min and then blended in 0.44 g of
graphite powder to obtain a homogeneous suspension. After vaporizing
water, about 0.2 mL of paraffin oil was added to the above mixture.
Finally, the mixture was mixed well for 70 min until a uniformly wetted
paste was obtained. After preparing the obtained paste, we pack it at the
end of a tube (i.d. 2 mm). The surface of the electrode is smoothed on a
piece of weighing paper. A new surface can be achieved by pressing
excess paste from the tube, removing excess, and mechanically refilling
the electrode surface. Also, the unmodified CPE was prepared by hand-
mixing of 0.5 g of graphite powder plus paraffin without any
modification.
M. Valian et al.
Fig. 5. FESEM micrographs of the Tb2Ti2O7 nanostructures prepared using (a, b) 1:1 (sample no. 6), (c, d) 1:6 (sample no. 2), and (e, f) 1:12 (sample no. 7) molar
ratio of oxalic acid to EG.
3. Results and discussion
3.1. FT-IR spectrum
In order to verify whether Tb2Ti2O7, has been successfully synthe­
sized, the sample was analyzed by FT-IR. Fig. 1 demonstrates the FT-IR
spectra from prepared nanostructure in the presence of oxalic acid and
calcined at 800 ◦ C for 2 h. The broad absorption at 3446 cm− 1 and a
weak band at 1600 cm− 1 allocated to the stretching vibrations of hy­
droxyl groups due to aerially adsorbed water [42]. The weak band at
1111 cm− 1 confirms the presence of oxygen-containing functional
groups related to the C–O bond in ethylalcohol on the surface of the
prepared nanostructures [43]. The characteristic peaks at the range of
400–580 cm− 1 can be attributed to the bending modes of the O-M-O and
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Talanta 247 (2022) 123593
1
the symmetric stretching modes of the M-O-M. The band at 420.02 cm−
was attributed to the vibration of the Ti–O–Ti bond [44–46].
3.2. XRD patterns
The XRD pattern of the nanostructures that were prepared under
various heat treatments of calcination is shown in Fig. 2a–c. As shown in
Fig. 2b, obtained sample in the presence of oxalic acid and calcined at
800 ◦ C for 2 h has a high degree of crystallinity and phase purity. The
different and sharp diffraction peaks observed in this pattern propose
cubic phase Tb2Ti2O7 with the JCPDS card No. 00-041-0363. A com­
parison of the diffraction peaks of the samples with different heat
treatments of Tb2Ti2O7 showed that the final product calcined at 700 ◦ C,
in addition to the Tb2Ti2O7 phase, there is an increase in the slight value
M. Valian et al.
Fig. 6. (a, b): TEM images of the Tb2Ti2O7 nanostructures prepared in the presence of oxalic acid at 800 ◦ C for 2 h with different magnification at two magnifications
(c) lattice fringes of prepared Tb2Ti2O7 nanostructures in HRTEM image.
of TiO2 with the JCPDS card No. 00-004-0477 as impurities. While in
sample 3 an increase in diffraction peak at 2θ = 27.508◦ is noted, which
is in accordance with the tetragonal TiO2 (JCPDS card No. 01-078-
1510). Scherrer equation was employed for the calculation of crystal­
lite diameter (Dc) of products [47]:
Dc = K λ/β cos θ, which K is the claimed shape parameter, which
generally catches an amount of about 0.9, λ is the wavelength of the X-
ray source used in XRD, and β is the width of the observed diffraction
line at its half-severity maximum. Therefore, the crystalline size related
to sample 2 was calculated at about 27.12 nm.
3.3. EDX analysis
For the purpose of determining of purity of the product, elemental
analysis by EDX was applied. The EDX analysis results in Fig. 3 confirm
the presence of Tb, Ti, and O elements in the chemical composition of
the sample generated in the attendance of oxalic acid and there were no
other peaks for impurities.
3.4. Microstructure analysis using FESEM and HR-TEM
In the Pechini method, the morphology and growth kinetics of par­
ticles can be affected by the different chelating agents [47,48]. Fig. 4a–f
illustrates SEM images of Tb2Ti2O7 nanostructures obtained in the
presence of the different chelating agents containing citric acid, oxalic
acid, and malonic acid, respectively. It is obvious when citric acid is
used, aggregated nanoscales with disordered shapes and different sizes
are organized (Fig. 4a and b). Nanostructures synthesized in the pres­
ence of oxalic acid have morphologic much like a blossoming flower,
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Talanta 247 (2022) 123593
which includes the placing of the nanoparticles in an absolutely sys­
tematically. These homogeneous nanoparticles stick together and mi­
crospheres form by traditional one-step self-assembly. The observations
prove that the semi-spherical microstructures are levelheaded in a
cohesive combination of the nanoparticles with a diameter lower than
15 nm (Fig. 4c and d). Whereas, the prepared TTNs in the presence of
malonic acid demonstrate inhomogeneous nanoparticles with small
particle size; however, a narrow distribution of the particles cannot be
observed (Fig. 4e and f). The diameter size of samples 4 and 5 appraised
from FESEM images is 84 and 47, commonly. The morphology of the
samples that were prepared to owe to the presence of dissimilar
chelating agents has been indicated in Scheme 1. It can be considered
that by utilizing oxalic acid in the role of a chelating agent with the most
favorable size, uniformity, and morphology among other chelating
agents, the uniform nanostructures with tiny scale can be designed. By
and large, the presence of carboxyl functional groups produces obstacles
with the purpose of memorizing nanoparticles from extra agglomeration
and the metal cation release rate is decreased. It seems that oxalic acid
can behave as the finest capping agent and result in increased germi­
nation rather than growing.
One of the important parameters to synthesize nanostructures by the
Pechini sol-gel method is applying the EG as a stabilization agent [49].
Also, its amount has major implications for controlling the size of
terbium titanate nanoparticles. It is obvious that EG in the presence of
organic acids with a large number of functional groups –COOH and –OH
can prevent the accumulation of nanoparticles by forming a polymer
resin. In the presence of oxalic, the polymer resin produced can
accommodate more cations than other chelating agents and, as the
germination increases, form nanostructures on a small scale. Scheme 3
M. Valian et al. Talanta 247 (2022) 123593

Fig. 8. Cyclic voltammograms of 5.0 mM [Fe(CN)6]3-/4- in phosphate buffer

(pH 7.0) at the surface of: (a) CPE and (b) TTN/CPE, scan rate 100 mVs− 1.

Fig. 7. (a): N2 adsorption/desorption isotherm and (b) Pore size distribution of

the optimized Tb2Ti2O7 nanostructures prepared in the presence of oxalic acid
Fig. 9. Cyclic voltammograms of (a) TTN/CPE in Britton–Robinson buffer (pH
at 800 ◦ C for 2 h (c) BET plot.
6.0), (b) CPE in the presence of MEF and (c) as (a) in the presence of 50
μM MEF.
shows the esterification of oxalic acid – ethylene glycol molecules. In the
continuation of the work, terbium titanate micrographs were used, and
connection with the formation of TTNs with the help of large amounts of
the relationship between the molar ratio of Acid: EG as a morphological
EG, some EG molecules can be selectively adsorbed on the surface of the
controlling agent and structural shape was investigated, while the
TTN nucleus through self-assembly with their specific predilection and
optimal capping factor of oxalic acid was introduced. For achieving this
eventually crystallize into a cube-like structure. This structure (samples
goal, samples 6 and 7 were prepared by exerting less (Fig. 5a and b) and
7) has a side width of ~1.721 μm and a height of ~339 nm with great
more amounts (Fig. 5e and f) of EG. By decreasing the molar ratio of
uniformity and narrow size distribution. These results confirm the
Acid: EG from 1:6 (Fig. 5c and d) to 1:1 (Fig. 5a and b), crystal growth
amount of the effects of EG on the size increases. It obviously indicates
and the distance between the nanoparticles increased obviously. In this
that the presence of an extra amount of chelating agents forms a
case, nano polymers are formed and lead to particles sticking together.
hydrogen bond with other acids that agglomerate the nanoparticles. It
Whereas, increasing the molar ratio from 1:6 (Fig. 5c and d) to 1:12
can be seen that sample 2, due to blossoming flower-like morphology,
(Fig. 5e and f), that illustrates agglomeration of the nanoparticles
smaller nanostructure size, and the favorable molar ratio was selected as
increased and regular cuboid-like morphology is observed. In
the optimum sample for electrochemical sensing applications.

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M. Valian et al.
Fig. 10. Differential pulse voltammograms of MEF at various percent of
Tb2Ti2O7 modifier at the surface of TTN/CPE.
Fig. 11. (a): DPV of 50 μM MEF at various pH values at the surface of TTN/CPE, (b): Electrochemical potential of MEF, Epa (mV) vs. pH at the surface of TTN/CPE
and (c): DPV Intensity of MEF, I (μA) vs. pH at the surface of TTN/CPE.
Scheme 2. Oxidation mechanism of MEF.
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Talanta 247 (2022) 123593
Fig. 6a and b illustrates the TEM images for Tb2Ti2O7 in various
magnifications that were designed by oxalic acid. It can be regarded that
the prepared sample possesses created a spherical morphology with a
size below 15 nm. HRTEM image of the prepared terbium titanate
nanostructures indicates in Fig. 6c. The distance between the two fringe
spacing was introduced by the parallel straight lines signifying the top
crystallinity level of the nanostructures. The results show that the dis­
tance between the two crystalline planes was 0.253 nm, which matched
well with the crystal planes (400) of Tb2Ti2O7.
3.5. BET study
The surface features and investigation of the pore structure have
been stated as the major characteristic that can directly show the pro­
ductivity of the sensors. The nitrogen adsorption/desorption isotherms
of the prepared Tb2Ti2O7 nanostructure are plotted in Fig. 7a. It is
explicitly observed that the N2 adsorption/desorption isotherms can be
categorized as a type III isotherm agreeing with the definition of IUPAC
assortments. H3-type hysteresis assigned to the mesopore or micropore
substances that categorized this specimen 2 [50]. The portrayed
M. Valian et al. Talanta 247 (2022) 123593

3.6. Electrochemical sensing application of Tb2Ti2O7 nanostructures

The electrocatalytic behavior of the TTN/CPE, the modified and

unmodified CPE was examined in a 5.0 mM redox probe containing [Fe
(CN)6]3− /4− couple using CV technique in 0.10 M phosphate buffer (scan
rate = 100 mV s− 1.(Fig. 8 demonstrates the cyclic voltammogram of the
nanostructured electrode in phosphate buffer (pH 7.0.(As can be seen in
Fig. 8b the oxidation peak of modified nanostructured becomes well
distinct, with enhanced current response and a decrease in ΔEp than the
bare CPE. This excellent electrocatalytic behavior is clear evidence of
the presence of the Tb2Ti2O7 nanostructures and excess available surface
area for the electrode that was modified by sample 2. Research has
shown that Tb2Ti2O7 (TTN) nanostructure is a potential material with
fine thermal solidity, low reactivity into the water, high capacitance,
high electrochemical stability, easy synthesis, high conduction, and
valence band offsets [51]. In general, nanoparticles, when combined
with carbon paste, produce synergistic effects that enhance their elec­
trochemical sensitivity. Furthermore, Tb2Ti2O7 creates a
well-conducting matrix with electric dipoles induced by magnetic
monopoles [52], which makes the construction of sensors useful.
Therefore, the TTN/CPE sensor was studied for the determination of
MEF. The cyclic voltammograms of both modified and unmodified
electrodes in Britton–Robinson buffer (pH 6.0) in the absence and
presence of MEF is shown in Fig. 9. As can be seen in Fig. 9c, the peak
current of the modified electrode by the Tb2Ti2O7 nanostructure is sharp
Scheme 3. Schematic of esterification of oxalic acid–ethylene gly­
and about 3 times greater than the bare CPE signifying the capability of
col molecules.
the nanostructure in the easiness of electron transfer reaction and the
creation of a suitable current signal of the sensor. Therefore, based on
isotherms in Fig. 7b and c indicate information on the BET specific
data the best electrocatalytic results for the oxidation of MEF were
surface area, the average pore diameter, and total pore volume with the
observed at TTN/CPE. Moreover, the catalytic effect of Tb2Ti2O7
measured value of 36.6 m2/g, 43.5 nm, and 0.18 cm3 g− 1, sequentially.
nanoparticles causes the improved oxidation of MEF and delicacy in
The average size of Tb2Ti2O7 nanostructure was assessed in the range of
analyte detecting. But to achieve a steady and acceptable response, the
1–46 nm by using the BJH analysis (Fig. 7b). The sample possesses a
best sensitivity for MEF, and to find the most optimal experimental
narrow pore size distribution containing mesopores (Fig. 7c).
factors, a series of experiments were performed at TTN/CPE surface.

1
Fig. 12. (a): Cyclic voltammograms of 40 μM MEF in Britton–Robinson buffer (pH 6.0) at the surface of TTN/CPE, using various scan rates: 20–120 mV s− (from
inner to outer) and (b): peak current, Ip (μA) vs. υ1/2.

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M. Valian et al.
Fig. 13. (a): Differential pulse voltammograms recorded in 0.2 M Britton–Robinson buffer at pH 6.0 after addition of MEF for obtaining final concentrations in the
range of 1.0 × 10− 2–4.0 × 102 μM and (b): plots of peak current as a function of MEF concentration (c): plots of current response and the linear relationship of low
concentrations.
3.6.1. Effect of the nanostructures amount
Certainly, the amount of modifiers affects the produced signals. The
electrochemical behavior of different amounts of Tb2Ti2O7 modifier was
investigated by DPV. Fig. 10 shows differential pulse voltammogram of
different amounts of Tb2Ti2O7 nanostructures (4, 8, 12, 16, and 20%, w/
w of Tb2Ti2O7 nanostructures to graphite powder) in Britton–Robinson
buffer (pH 6.0) containing 50 μM MEF. It can be seen that the DPV signal
was promptly increased when the amount of the Tb2Ti2O7 nanostructure
in the paste was increased to about 12%. Afterward, after 12%, the peak
current was slightly decreased. Such behavior of this kind may be
assigned to the fact that higher loadings on the modifier layer reduce the
electron transfer rate by increasing the resistance of the electrode
(Fig. 10d and e). As a result, the nanostructure amount of 12% was
employed for the construction of the modified nanostructured electrode.
3.6.2. pH dependence study
One key parameter in electrochemical investigations in pH-
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Talanta 247 (2022) 123593
dependent electrocatalytic systems is the pH value. The effect of pH in
sensing studies of the electrolyte containing 50 μM MEF was recorded by
differential pulse voltammetry (DPV) for TTN modified electrode with
pH amounts over the range from 3.0 to 11.0 (Fig. 11a). It can be
observed that with increasing pH, the oxidation potential of the MEF
transfer to negative potential values which is a consequence of the
deprotonation involved in the oxidation process (Fig. 11b). It is to be
noted that there is an exact relationship between oxidation potential
values of the modified electrode and pH with the slope equal to − 61.4
mV pH− 1, which is close to the Nernstian value (59.1 mV pH− 1). This
demonstrates that the electrochemical reaction obeys Nernst’s equation
(Eq. (1)) and an equivalent number of electrons and protons participate
in electrode reaction [53–56].
[ ]
(1)
◦
Ep = E + (59.1/n)log (Ox)a /(R)b − (59.1 m / n)pH
Epa (mV vs. Ag/AgCl) = 996.13 − 61.4 pH R2 = 0.99
M. Valian et al. Talanta 247 (2022) 123593

Table 2 cyclic voltammograms were considered in the electrolyte solution (pH

Comparative feature of electrochemical sensors for the determination of MEF. = 6.0) over different scan rates of 20–120 mV s− 1 in the attendance of
Electrode Technique pH Linear range LOD Ref. MEF (Fig. 12a). As illustrated in Fig. 12b, the peak current response of
(μM) (μM) MEF increases rectilinearly with ν1/2 that proposed an ordinary
Cu2+Y/ZMCPEa DPV 10 0.30–100 0.040 [57] diffusion-controlled process [53,54].
Fe (III)-SBMCPEb DPV 3.5 0.02–150 0.020 [56]
GCEc DPV 5.0 1.00–1000 0.15 [58] 3.6.4. Designation of MEF at the surface of TTN/CPE
BDDEd DPV 6.0 0.50–100 0.078 [54] The primary objective of this study is to design a very susceptible
MWCNTs–NHNPs/ DPV 7.0 0.10–85.0 0.040 [59]
GCEe
procedure for the designation of MEF. DPV signals were considered to
MWCNTs-CHT/GCEf DPV 7.0 4.00–200 0.66 [60] assess the capability of the intended sensor to analyze the purpose, at
CdO/PANI/mpg- DPV 7.4 0.20–400 0.045 [55] different MEF concentrations from 1.0 × 10− 2–4.0 × 102 μM. Fig. 13a
C3N4/GCEg exhibits the DPV current responses of the TTN/CPE electrode for the
NiO-SWCNTs/DDPM/ SWV 8.0 1.00–600 0.50 [61]
oxidation of MEF in different concentrations. Furthermore, Fig. 13b
CPEh
SWNT/GCEi SWV 7.2 0.10–35.0 0.013 [62] displays unequivocally that the chart of the oxidization current ac­
TTN/CPE DPV 6.0 0.01–400 0.0024 This cording to MEF value indicated two linear detection ranges from 1.0 ×
work 10− 2–1.6 × 102 μM and 1.6 × 102–4.0 × 102 μM with the linear
a
Copper (II) doped zeolite modified carbon paste electrode. regression equations of the Ipa (μA) = 0.056C (μM) + 0.31 (R2 = 0.99)
b
Carbon paste electrode modified with Fe (III) schiff base. and Ipa (μA) = 0.021C (μM) + 6.2 (R2 = 0.99), respectively. From the
c
Glassy carbon electrode. measured first linear dynamic range, the limit of detection (3σ) of MEF
d
Boron-doped diamond electrode. at the surface of TTN/CPE has been assessed at 2.4 nM. The analytical
e
Glassy carbon electrode modified with nickel hydroxide nanoparticles/ achievement of this strategy in terms of pH designation, detection limits,
multiwalled carbon nanotubes. or linear amplitudes for MEF concentrations compared to other results of
f
Glassy carbon electrode modified with multiwalled carbon nanotube/chi­ published electrochemical analysis, indicates that the analytical per­
tosan composite. formance of the TTN/CPE electrode is analogous or even better
g
Glassy carbon electrode modified with three-dimensional mesoporous
(Table 2). Also, this sensor is comparable to other MEF sensors in terms
polymeric graphitic-C3N4/polyaniline/CdO nanoparticles.
h of creating a specific morphology with the help of a plain preparation
Carbon paste electrode modified with nickel oxide nanoparticles-single wall
carbon nanotubes as conductive mediator and 2, 4-dimethyl-N/-[ 1-(2, 3-dihy­ method without the use of high-priced or noxious raw materials and a
droxyphenyl) methylidene] aniline (DDPM) as electro-catalyst. short time for MEF analysis. This reasonable investment may be ascribed
i
Glassy carbon electrode modified with single walled carbon nanotubes. to four key arguments for instance (1) Employing the Tb2Ti2O7NP with
extraordinary intrinsic characteristics in the structural body; (2) The
synthesis of titanate nanostructure as a potential novel kind of sensors
Table 3 with the capability to high analytical performance; (3)The capability of
Effect of various interferences on the differential pulse voltammetric response of nanoparticles prepared with morphology similar to a blossoming flower
50 μM MEF at the surface of TTN/CPE. as an efficient platform in increasing the surface; (4) Creating an active
Foreign substances Tolerance level (μM). substrate on the surface of the modified electrode which resulted in the
K+, Na+, NH+
proper oxidation of MEF on the surface.
4 , Cl 5000
−

Mg2+, CO32− , SO42− , proline, methionine 3000

L-alanine, Glucose 1300 3.6.5. Repeatability, stability, and selectivity examination
Uric acid, Fructose 900 One of the prime elements in evaluating sensor performance is quick-
to-surface renewal after each use. Thus, the repeatability of the analyt­
ical signal was considered by DPV information, from five individually
Table 4 TTN/CPE platforms. The relative standard deviation (RSD) amounts of
Detection of MEF in real samples at the surface of TTN/CPE. sensing materials, at concentrations of 50 μM MEF, were estimated at
SAMPLE ADDED (μM) FOUND (μM) RECOVERY (%) 2.9% indicating the repeatability of the TTN/CPE for the MEF evalua­
tion. Likewise, the stability of the TTN/CPE modified platforms was
HUMAN BLOOD SERUM
1 0.00 Not detected – assessed over a 2-week period. Successive DPV determination of a so­
2 2.00 1.90 95.0 lution containing 50 μM MEF registered during the period revealed the
3 10.0 9.20 92.0 MEF peak potential was untouched and the current signals decreased
4 20.0 21.4 107
less than 4.15%. The effect of various interfering species on the behavior
TABLET
1 0.00 0.47 –
of MEF (50 μM) with pH = 6.0 was investigated by DPV. The findings
2+ 2−
2 4.00 4.50 101 suggest that common ions such as Na+, K+, NH+ 4 , Mg , Cl , CO3 , and
−

3 5.00 5.48 100 SO2−

4 have no efficacy on the oxidation current of MEF. Furthermore, the
4 6.00 6.40 98.8 interference of some biological fluids such as L-alanine, glucose, fruc­
WASTEWATER
tose, and uric acid and some pharmaceutical compounds such as proline
1 2.00 2.20 110
2 3.00 2.80 93.3 and methionine did not meaningfully affect the height of the peak cur­
3 6.00 6.30 105 rents. The results summarized in Table 3, demonstrate that the sug­
gested nanostructured sensor has an acceptable selectivity for the
determination of MEF in the presence of a high concentration of these
Furthermore, in Fig. 11c, the variation of peak current versus pH has interference species.
schemed. It was disclosed that the maximum of the peak current value
was accomplished in the pH = 6.0. This suggests that pH 6.0 can be used
3.7. Real sample analysis
as an ideal pH for the determination of MEF. Also, the proposed redox
reaction mechanism of MEF has been shown in Scheme 2.
In the last stage, the applicability of the TTN/CPE was studied to the
analysis of MEF in human blood serum, tablet, and pharmaceutical In­
3.6.3. Scan rate dependence study
dustry wastewater samples. The standard addition method was utilized
To further study the electrocatalytic demeanor of the TTN/CPE, the
to conduct analysis and DPV signals were registered. The values of the

11
M. Valian et al.
analytical parameters obtained for real samples according to this
method are reported in Table 4. The recovery percentage terms of the
method for blood serum, tablet, and wastewater samples were achieved
between 92.0 and 107%, 98.8–101%, and 93.3–110%, respectively. The
recoveries results displayed that the suggested methods could be effi­
ciently used for the detection of trace amounts of this compound in
biological conditions, medicinal preparations, and wastewater.
4. Conclusions
For the first time, Tb2Ti2O7 nanostructures were successfully syn­
thesized via the modified pechini method and used for the analysis of
MEF in real samples. The investigations showed the architecture, size,
and high porosity of these nanostructures amended and managed by
modifying the varied organic acid, amount of stabilization agent, and
temperature of calcination. The purpose of the present project was to
evaluate the electrochemical sensing of MEF by TTN/CPE using CV and
DPV techniques. In this work, CPE was revived using small amounts of
new Tb2Ti2O7 nanostructures to produce a more reasonable surface
area, which resulted in faster electron transfer and increased electro­
catalysis effect. The proposed sensor demonstrated a low detection limit
(2.4 nM) with a high linear dynamic range (1.0 × 10− 2–4.0 × 102 μM).
This sensor was used for the analysis of real samples successfully and
finally obtained good recovery percentages. Moreover, the TTN/CPE
revealed stability in the long run and good reproducibility. As a result,
terbium titanate nanostructures are a favorable candidate for sensitive
monitoring of anti-inflammatory drugs in real complicated samples.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgment
Authors are grateful to the council of Iran National Science Foun­
dation; INSF (97017837) and University of Kashan for supporting this
work by Grant No (159271/MV2).
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