Microchemical Journal 185 (2023) 108281

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Microchemical Journal
journal homepage: www.elsevier.com/locate/microc

Review Article

Recent electrochemical sensors and biosensors for toxic agents based on

screen-printed electrodes equipped with nanomaterials
Masoud Negahdary a, *, Wilson Akira Ameku a, Berlane Gomes Santos a, Irlan dos Santos Lima a,
Thawan Gomes de Oliveira a, Mesaque Carvalho França b, Lúcio Angnes a, *
a
Department of Fundamental Chemistry, Institute of Chemistry, University of São Paulo, Av. Prof. Lineu Prestes, 748, São Paulo 05508-000, Brazil
b
Department of Analytical Chemistry and Physical Chemistry, Federal University of Ceara, Avenida Mister Hull, s/n – Pici, Fortaleza, State of Ceará 60455-760, Brazil

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

Keywords: Fast and accurate detection of toxic substances can effectively increase the quality of human life, life expectancy,
Toxic substances and environmental protection. So far, many electrochemical (bio)sensors have been designed to provide optimal
Electrochemical sensors (simplicity, low cost, high selectivity, and high sensitivity) detection of toxic substances. Here, the latest (2021
Screen-printed electrodes (SPEs)
and 2022) electrochemical (bio) sensors involving nanomaterials-based SPEs for detecting toxic species are
Nanomaterials
Health promotion
categorized and reviewed. The main application of nanomaterials was found as an increasing diagnostic sensi­
tivity agent. Toxic substances were investigated and categorized into several groups: toxins, toxic inorganic
species, pesticides and other organic residues, and drugs. Evidently, toxicity depends on the dose of each sub­
stance, and unwanted doses, even for drugs. The specific features of diagnostic platforms, the application of
various nanomaterials, and diagnostic strategies were included. Moreover, the crucial specifications of all
electrochemical (bio)sensors that have recently been developed to detect toxic substances have been presented in
several tables considering the type of analyte.

1. Introduction
Today, entering toxins, toxic inorganic species, pesticides and other
organic residues, and drugs into human life are unavoidable. Undoubt­
edly, these substances have brought important advantages in many as­
pects of life and even economic activities, improving human life quality
[1–3]. Nevertheless, the evidence and epidemiological studies indicate
that the improper use of toxic substances can be a huge concern for
human health and the environment. Toxic agents can lead to death,
temporary disability, or permanent damage in humans, animals, and
plants by affecting physiological, metabolic, or genetic routes. These
include inappropriate doses of all chemicals regardless of origin or
production method [4,5]. The toxicity of a substance depends on three
factors: chemical structure, the amount of absorption of the substance by
the body, and the body’s ability to detoxify the substance (change it to
less toxic substances) and excretion of it from the body [6,7]. In one
category, toxic substances include pesticides, industrial chemical poi­
sons, organic compounds, inorganic compounds, and toxic pollutants in
the air. The body acts to be particularly sensitive to the effects of
chemicals when the body’s organs develop, so if contact with toxic
chemicals occurs during this period, it can cause permanent changes in
physical function [8,9]. However, poisoning may not reflect any specific
symptoms for a long time. Avoiding toxic chemicals is especially
necessary when protecting infants and children uniquely vulnerable to
toxic agents [10]. Also, recent research confirmed that even short-term
exposure to some toxic agents could lead to cancer, infertility, learning
disabilities, and other serious health problems [11]. Overall, the most
dangerous damages related to toxic substances on the body can include
disruption of the hormonal system, disorders leading to decomposition
or non-decomposition (accumulation) of toxic substances, reproduction
disorders, DNA damage, or cancer [12,13]. Monitoring toxic agent levels
at various points in industrial and recycling processes, in effluents and
wastewaters, in industrial, agricultural, and urban areas have become
necessary in recent years due to growing concern over the toxic effects of
these substances in the environment and food industries [14,15]. In
addition, methods that are quick to react, inexpensive, portable, suffi­
ciently sensitive, and have long-life stability are needed to monitor
environmental and industrial safety [16]. The detection procedure using
standard methods is typically time-consuming, and laboratory ap­
proaches to detect and identify target molecules need expensive

* Corresponding authors.
E-mail addresses: mnegahdary@iq.usp.br (M. Negahdary), luangnes@iq.usp.br (L. Angnes).

https://doi.org/10.1016/j.microc.2022.108281
Received 26 September 2022; Received in revised form 29 November 2022; Accepted 1 December 2022
Available online 5 December 2022
0026-265X/© 2022 Elsevier B.V. All rights reserved.
M. Negahdary et al.
equipment and trained personnel. The employment of electrochemical
sensors is a rapid, inexpensive, and portable approach for detecting toxic
analytes. Electrochemical sensing technology reached to advanced
significantly over the past few decades and has emerged as a vital area of
research and commercialization [17–19]. In actuality, electrochemical
(bio)sensors are systems that mainly contain a recognition component
(specifically high-selective against analytes) and a signal transducer (to
transform the detected signal into a measured signal) [20–22]. The
electrochemical (bio)sensor can only respond to selected analytes thanks
to the recognition component’s unique and defined architecture
[23–25]. Using electrochemical sensors in industry, environment, and
health monitoring reported while identifying various diseases is wide­
spread [26–34]. Amperometric, potentiometric, and impedimetric sen­
sors are the three main categories of electrochemical sensors [35,36].
Creating smaller, more precise, and sensitive electrochemical sensors
containing the convergence with nanotechnology is required for accu­
rate measurements [37–42]. Due to many benefits, including unique
electronic, mechanical, and catalytic properties obtained from the
increased surface area to volume ratio at the nanoscale, nanomaterials
have been widely used in the preparation and construction of electro­
chemical sensors over the past two decades [43–49]. The nanoscale
features have significantly altered the patterns of sensor development.
Fig. 1 presents the most important components of electrochemical (bio)
sensors involving nanomaterials-based SPEs for detecting toxic species.
SPEs have several benefits, including low cost, design flexibility, the
ability to manufacture from various materials, and the possibility to set
up with the minimum volume of (bio)recognition element components
and analytes in three-electrode systems. Furthermore, this signal
transducer has many working. Another benefit is the potential for
connection to portable apparatus, which enables in-situ analysis of
desired analytes. SPEs also prevent time-consuming cleaning proced­
ures. In this review, the analytes included in electrochemical sensors
contained toxic substances. In included (bio)sensors, the working elec­
trode surface or other detection components were modified with various
nanomaterials, including carbon nanostructures, gold nanostructures,
other nanostructures, or even nanocomposites. Here, very diverse and
different diagnostic platforms have been reported. Enzymes, peptide
sequences, or nucleotide sequences were usually used as the
Fig. 1. Schematic illustration of electrochemical (bio) sensors involving nanomaterials-based SPEs for detecting toxic species.
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Microchemical Journal 185 (2023) 108281
biorecognition element in biosensors employed to detect toxic sub­
stances. In other electrochemical sensors, the presence of chemicals and
electrolytes effectively directed the detection process.
2. Electrochemical sensors developed for the detection of toxins
Toxins are poisonous compounds created by living things like bac­
teria, fungi, plants, and animals. They are created naturally and without
human contribution [50,51]. Generated from Fusarium species, Zear­
alenone (ZEA) is a secondary metabolite known as an estrogenic
mycotoxin. ZEA is generally found in foods obtained from contaminated
crops and has recently been considered an endocrine disruptor (changes
in estrogen levels), contributing to the development of some cancers and
disorders in the reproductive system, which can also lead to fertility
problems in animals and humans.
In a research, an electrochemical aptasensing platform was devel­
oped to detect ZEA using a SPE electrode modified with MXene
(Ti3C2Tx)/Chitosan film [52]. Firstly, Ti3C2Tx was synthesized by
etching off aluminum from a mixture of MAX powder (Ti3AlC2) and
hydrofluoric acid. The design of this aptasensor consisted of preparing a
modified SPE with Ti3C2Tx/Chitosan films and then performing the
immobilization of an amino-functionalized aptamer as the bioreceptor
on the surface of the electrode. The enhanced and optimized electrode
surface area created by advanced materials, such as Ti3C2Tx, provides
the sensitive detection of ZEA. Additionally, this material type also
possesses great chemical stability, electrical conductivity, and hydro­
philic affinity, which are important features for application in electro­
chemical (bio)sensors. Here, OH groups related to Ti3C2Tx improved the
performance of the working electrode, and the signal amplification was
processed in the presence of a thin layer of chitosan on the surface of the
SPE. It was observed an increase in surface resistance related to electron
transfer after the immobilization of aptamer strands on the surface. A
similar and sharper phenomenon occurred in the presence of various
concentrations of ZEA due to electronic surface inhibition affected by
bio-interactions on the surface of SPE. The electrochemical impedance
spectroscopy (EIS) analysis confirmed that the presented aptasensor
could detect the analyte in a linear range from 1 fg ml− 1 to 1 ng ml− 1; the
reported limit of detection (LOD) was about 1 fg ml− 1.
M. Negahdary et al.
In another research, an aptasensor based on Au NPs@Ce-1, 3, 5-tri­
formylphloroglucinol (Tp) 2, 2́ -bipyridine-5, 5́ -diamine (Bpy) covalent
organic framework (COF) Tp-Bpy was developed to determine the ZEA
in cornflour [53]. In order to construct this aptamer-based biosensing
platform, Au NPs@Ce-TpBpy COF nanocomposite was synthesized,
mixed with chitosan, and subsequently dropped on a SPE surface. Then,
a thiol-functionalized ZEA aptamer as the bioreceptor was immobilized
on the modified surface of the SPE by the mentioned nanocomposite.
The aptamer strands bound to the sites contain the Au atoms through the
Au-S covalent bond. After the immobilization of aptamer, to prevent and
block unwanted interaction between the surface of Au and aptamer
molecules, the 6-mercaptohexanol (MCH) was used. Here, the chro­
noamperometry technique was used as the detection method to measure
the reduction current of hydrogen peroxide (H2O2) catalyzed by Au
NPs@Ce-TpBpy COF nanocomposite on the surface of the signal trans­
ducer. As the ZEA concentration increased, the H2O2 reduction current
decreased and provided a correlation between the decreased levels for
the H2O2 signal in contrast to ZEA concentrations. The linear detection
range for the presented aptasensor was determined from 1 to 10 ng
mL− 1, and the calculated LOD was about 0.389 pg mL− 1.
Myotoxins are small peptides found in the venom of some snakes and
lizards. The toxicity of this toxin initiates a non-enzymatic mechanism
that leads to severe muscle necrosis in target organisms [54]. In a
research, a biosensing platform was developed for the detection of three
myotoxins (deoxynivalenol (DON), 3-acetyldeoxynivalenol (3-ADON),
and 15-acetyldeoxynivalenol (15-ADON)) [55]. Here, a 3D bio-printed
electrode was applied as the signal transducer, while the working area
electrode was made from carbon nanofiber. In summary, Dulbecco’s
minimal essential medium cell culture solution was prepared and mixed
with lithium phenyl(2,4,6-trimethyl benzoyl)phosphinate as a photo-
initiator. Then, a mixture containing photosensitive features was pro­
vided. After a desired time-controlled thermal cycle, the gelatin meth­
acryloyl was obtained. In the next step, a solution containing the
dissolved carbon nanofiber in the phosphate buffered saline (PBS) was
prepared and added to the gelatin methacryloyl. Finally, human lung
cancer cells A549 with the adjusted concentration were added, and a
Fig. 2. Elements contributed to a multiplexed SPE-based sensing platform for determining several myotoxins; License Number: 5,386,150,865,800 [55].
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hydrogel bio-nanocomposite was achieved (Fig. 2). The surface (carbon)
of the prepared 3D bio-printed electrode was modified with gold
nanoparticles (AuNPs) through an electrodeposition procedure. Then,
the hydrogel bio-nanocomposite was dropped on the surface of the
mentioned signal transducer and dried by lighting. The electrochemical
measurements were monitored through EIS, using ferro/ferricyanide (Fe
(CN)3–/4–
6 ) as the redox marker. The presence of analytes showed a
different electron transfer rate on the surface of the signal transducer.
The analyte concentrations interacted with cancer cells A549, and by
incrementing the concentrations of analytes, the electron transfer rate
decreased.
Aspergillus species, including Aspergillus flavus, Aspergillus para­
siticus, and Aspergillus nomius produce Aflatoxins (AFs), which are
highly toxic metabolites (mycotoxins). Wheat, barley, and rice are often
more resistant to these fungi than corn, peanuts, or pistachios, which are
typically more susceptible to these mycotoxins [56]. AFs contamination
of food, including eggs, milk, and dairy products, can cause serious
health problems, including reduced immune response, damaged liver
functions, and increased probability of acquiring infections that are
considered carcinogenic risk factors. Four main AF types include B1, B2,
G1, and G2 [57,58]. AFB emits blue light under the influence of ultra­
violet light, which is a reason for this AF to be marked with the letter B.
AFG emits green light under the influence of ultraviolet light, which is a
reason for this AF to be marked with the letter G. In addition, AFG1 and
AFB1 are more harmful. They have an extra double bond (on carbons 8
and 9) than AFG1 and B1 [59,60]. After consuming food contaminated
with AFB1 and B2, AFM1 and AFM2 (a hydroxylated form of AFB) are
produced as an outcome of enzyme activity primarily found in the liver,
which is less toxic than AFB.
The finding of naturally chain antibodies comprising a highly stable,
soluble, and organic solvent tolerable single antigen-binding V-domain,
(namely as nanobody: 15 kDa and the dimension of 2.5×3×4 nm3), has
led to a new generation of immunosensors and antitumor therapeutics
[61–63]. In a study, Tang et al. developed an immunosensor using a
screen-printed carbon electrode (SPCE) and a nanobody for electro­
chemical sensing of AFM1 in milk [62]. Due to its hepatotoxicity and
M. Negahdary et al.
potential carcinogenicity, AFM1 has been considered a carcinogen
agent, and its maximum permitted levels in milk are defined from 0.025
to 0.5 μg L–1 [64,65]. The mentioned research produced nanobodies by
immunizing alpacas with anti-AFM1 monoclonal antibodies. Then, the
AFM1 nanobodies were immobilized on the electrode surface through
the 1-ethyl-3-(3-di-methylamino-propyl) carbodiimide hydrochloride
(EDC)/N-Hydroxysulfosuccinimide sodium salt (NHS) cross-linking, and
AFM1 detection was performed by a competitive method where both
AFM1 and nanobodies competed for the interaction with antibodies in
the solution. The difference between electrochemical currents before
and after binding with the analyte represented the sensor response. In
the presence of AFM1, the analyte molecules interacted with antibodies
occupying the antigen-binding site. Therefore, antibodies could not
interact with the immobilized nanobodies; thus, they were eliminated
by washing from the sensing platform. Consequently, the capture of
horseradish peroxidase (HRP)-labeled secondary antibodies in the sub­
sequent step was avoided by decreasing the 3, 3′ , 5, 5′ -tetrame­
thylbenzidine (TMB) signal in the catalyzed reaction (Fig. 3).
Nevertheless, in the AFM1 absence, the signal recorded in the blank
medium did not change significantly. The designed sensor could be
stored for nine weeks at 4 ◦ C showing a slight loss of the initial activity
(5 %) and confirming the desired stability of the employed nanobody
over time. The presented immunosensor could detect the analyte in a
linear concentration from 0.25 to 5 ng mL− 1, and the determined LOD
was about 0.09 ng mL− 1.
In another research, molybdenum disulfide quantum dots (QDs)-
MOF nanocomposite was applied to build an electrochemical sensor for
AFM1 [66]. For the sensor’s construction, the MoS2-UiO-66-NH2 was
prepared and drop-casted on the surface of a SPCE working area. After
this step, a solution containing the antibody as the bioreceptor was
immobilized on the electrode surface considering enough incubation
process. Subsequently, the prepared immunosensor was used to detect
AFM1 in spiked milk samples using the EIS technique. It was observed
that with increasing concentrations of AFM1, an increase in charge
Fig. 3. Schematic illustration of an immunosensor designed based on SPCE to determine the various concentrations of AFM1; production procedure of AFM1
nanobodies (a), design of the sensing platform (b), and electrochemical analysis related to various concentrations of analyte (c); License Number:
5,379,631,438,629 [62].
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Microchemical Journal 185 (2023) 108281
transfer resistance (Rct) value was found. The increase in the Rct value
occurred due to the formation of the antigen-antibody complex on the
electrode surface, creating a kinetic barrier that hinders the charge
transfer process between the surface of the signal transducer and elec­
trolyte. The accessible detection range was from 0.2 to 10 ng mL− 1, and
the LOD determined about 0.06 ng mL− 1.
In recent research, carbon black (CB) is used as a surface modifier in
the design of sensing platforms due to the chemical stability, fast het­
erogeneous electron transfer rate, and considerable signal amplification
effect compared to carbon nanotubes, graphene, and gold-based nano­
materials [67,68]. The CB can be used with other nanomaterials or
polymers to improve electrochemical performance by enhancing elec­
trical conductivities, charge rate, and electroactive surface area [67]. In
a study, a SPE was modified with CB to fabricate an immunosensor in­
tegrated into a smartphone application and a commercial miniaturized
potentiostat for the accurate and sensitive detection of AFB1 in cereals
[68]. The established immunosensor worked using indirect competitive
assays. The AFB1 antigens competed for antibodies, either free in the
medium or immobilized on the surface of magnetic beads (MBs). In case
of a negative result, AFB1/MBs interacted with antibodies, allowing the
formation of immune complexes with HRP-labeled secondary immu­
noglobulin G (HRP-sec-IgG) on the surface of the signal transducer
(Fig. 4); thus, when they were attracted to the electrode surface by
assisting an external magnet, a strong electrochemical current obtained
from the enzymatic reaction between HRP, hydroquinone, and H2O2. On
the other hand, the AFB1 presence occupied the antibodies’ antigen-
binding site and avoided the formation of the immune complexes on
the MBs’ surface. This event led to a decrease in the electrochemical
current transferred from the electrode surface. The sensor reached the
LODs equal to 13 and 24 pg mL− 1 and a low relative standard deviation
(RSD) of 3.7 % and 4 % in buffer and spiked corn extract, respectively,
indicating wanted performance.
Table 1 presents the most important features of electrochemical
sensors designed to detect toxins. This table includes the latest research
M. Negahdary et al.
Fig. 4. Schematic illustration of the fabrication of an immunosensing platform integrated into a smartphone application and a commercial miniaturized potentiostat
for the accurate and sensitive detection of AFB1; License Number: 5380030651147.
based on SPEs as the signal transducer.
3. Electrochemical (bio) sensors for the detection of toxic
inorganic species
The poisonous impact of various inorganic species (especially metal
ions) on living things is known as a health-threatening factor [73].
Environmental pollution and human exposure to various inorganic
species, mainly obtained from heavy metals like lead, cadmium, and
mercury, have become severe and widespread issues worldwide [74].
Unfortunately, since these metals have been discovered and developed
over the past fifty years, they are used more frequently in industrial
processes and manufacturing [75]. Daily exposure to these toxic ions
occurs indirectly for humans through various biological substances,
food, drink, and air. Given this emerging concern, a SPE modified with
cobalt oxide (Co3O4) NPs@graphitic carbon was employed to detect
Pb2+ and Cd2+ ions simultaneously [76]. Co3O4 NPs@graphitic carbon
nanocomposite was prepared by a facile citrate–nitrate thermal treat­
ment. Firstly, cobalt nitrate hexahydrate and anhydrous citric acid were
mixed in water, and the thermal treatment was subsequently processed.
Here, it was possible to obtain homogeneous dispersed Co3O4 on
graphitic carbon structure, and a carbon-based material on Co3O4 NPs
could improve the sensing activity. At this point, the SPE surface was
modified with the mentioned Co3O4 NPs@graphitic carbon nano­
composite. The EIS measurements showed a significant decrease (39 %)
in Rct values compared to bare SPE, indicating the conductivity
improvement and a faster electron transfer rate for SPE/Co3O4@gra­
phitic carbon nanocomposite. After optimizing the experimental pa­
rameters, differential pulse anodic stripping voltammetry (DPASV)
measurements were executed while a proportional enhancement of
anodic peak current with increasing Pb2+ and Cd2+ ions concentration
was reported. The linear detection range was from 0 to 140 parts per
billion (ppb) for both toxic metals, and the LOD was 3.2 ppb and 3.5 ppb
for Pb2+ and Cd2+, respectively.
In another study, an electrochemical sensing platform was developed
to determine various concentrations of Pb2+ using a modified SPCE with
dopamine polymer doped polypyrrole (PDA-PPy) [77]. Here, the surface
of the signal transducer was modified PDA-PPy through the drop-casting
procedure. Then, by employing the square wave anodic stripping vol­
tammetry (SWASV) technique in the HAc-NaAc buffer, the analyte
monitoring followed (Fig. 5). It should be considered that the PDA-PPy
hydrogel interacted with various concentrations of the analyte, where
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Microchemical Journal 185 (2023) 108281
each element of the hydrogel demonstrated a function in the Pb2+
adsorption. According to research, Pb2+ may be coordinated with pyr­
role nitrogen at a ratio of 1:4 since PPy and Pb2+ have a higher binding
affinity than other metal ions. As a result, PDA-PPy hydrogel offers many
active sites that may effectively absorb Pb2+ onto the electrode surface
through a process known as competitive adsorption. In the presented
research, the adsorbed Pb2+ was reduced to Pb during the enrichment
process. The electrochemical analysis of the analyte confirmed that the
designed sensor could assay various concentrations of Pb2+ in a linear
range from 3 to 300 μg L− 1 with a signal-on pattern.
Toxicity resulting from Arsenic (As) is a global concern in human
health due to its directed challenges, including cancers related to skin,
lung, bladder, and even cardiovascular diseases. The most common
forms of As in drinking water are As3+ and As5+. In a study, determining
As3+ shadowed through electrochemical measuring in the presence of a
modified SPCE with benzotriazole-rGO [78]. Carbon nanomaterials
have excellent properties, including high conductivity, a large surface
area-to-volume ratio, and an improving role in the charge transfer be­
tween the analytes and the signal transducer. So far, applying these
nanomaterials has opened the way to several advances in electro­
chemical sensors [79]. GO sheets are an excellent multifaceted platform
for inserting functional groups to obtain sensitive interfaces for specific
interactions with target analytes. Here, GO was synthesized through
Hummer’s method, and then the GO in a reduced form was function­
alized with Benzotriazole and modified the surface of the SPCE to detect
As3+. The Fourier-transform infrared (FTIR) analysis confirmed the
presence of C–O, C–O–C, C-OH, C– – C, C–– O, N–
– N, and N–N in­
teractions related to the Benzotriazole-rGO surface. In addition, the
scanning electron microscopy (SEM) morphology analysis showed
forming of the nanostructure from the compound related to the uniform
dispersion of Benzotriazole in the rGO molecules. The modified surface
of SPCE was applied to quantify the analyte in tap water samples. The
DPV technique was used for electrochemical measurements, and along
with enhancing the various concentrations of analyte, the anodic peak
current was enhanced regularly, which exhibited a signal-on behavior.
This sensing platform could detect As3+ in a linear range from 2 to 40
nmol/L.
In an investigation, Hg2+ and Cr6+ ligands (thymine and carbohy­
drazine), were covalently introduced to the GO (thymine-GO-carbohy­
drazine) for the selective capturing of trace metals [80]. The resulting
nanocomposite was utilized to modify a glassy carbon electrode (GCE)
and also a SPE for Hg2+ and Cr6+ multiplexed detection (followed by
M. Negahdary et al. Microchemical Journal 185 (2023) 108281

Table 1
Electrochemical (bio)sensors involving nanomaterials-based SPEs for the detection of toxins.
Analyte Analyte origin Type of Nanomaterial Nanomaterial Electrode Detection Application Detection LOD Ref.
SPE (s) (s) position (s) configuration technique to samples range

ZEA Fusarium and SPE MXene-Chitosan On the surface Aptamer-based EIS Cow milk/ 1 fg mL− 1 1 fg mL− 1
[52]
Gibberella nanocomposite of the working biosensor: the Corn –1 ng mL− 1
species electrode surface of SPE was
modified with
nanomaterial (s) and
then an amine-
functionalized
aptamer was
immobilized on the
surface and applied
as the biorecognition
element for the
detection of analyte.
ZEA Fusarium and SPE Au NPs@Ce- On the surface Aptamer-based CA Crops 1–10 ng 0.389 pg [53]
Gibberella TpBpy COF of the working biosensor: the mL− 1 mL− 1
species nanocomposite electrode surface of SPE was
modified with
nanomaterial (s) and
then a thiol-
functionalized
aptamer was
immobilized on the
surface and applied
as the biorecognition
element for the
detection of analyte.
Okadaic Dinoflagellates SPE FL-WO3/ On the surface Antibody-based PEC CRM-DSP- 0.01–60 0.007 ng [69]
Acid species UCNPs/NaYF4: of the working biosensor: the Mus-c ng mL− 1 mL− 1
Yb, Tm electrode surface of SPE was muscle
nanostructures modified with tissue
nanomaterial (s) and
then the antibody
was immobilized on
the surface and
applied as the
biorecognition
element for the
detection of analyte.
Okadaic Okadaic acid: SPE CB On the surface Antibody-based DPV —* Okadaic Okadaic [70]
acid/ Dinoflagellates nanomaterial of the working biosensor: the acid: acid:
Domoic species/Domoic electrode surface of SPE was 0.27–3.9 0.15 ng
acid acid: Algae and modified with ng mL− 1/ mL− 1/
Accumulates nanomaterial (s) and Domoic Domoic
species then the antibody acid: 4–72 acid: 1.7
was immobilized on ng mL− 1 ng mL− 1
the surface and
applied as the
biorecognition
element for the
detection of analyte.
AFM1 Aspergillus/ SPCE AIdnb On the surface Antibody-based CA Milk 0.25–5 ng 0.09 ng [62]
Aspergillus of the working biosensor: the mL− 1 mL− 1
flavus/ electrode surface of SPE was
Aspergillus modified with the
parasiticus/ nanobody and then
Aspergillus the antibody was
nomius immobilized on the
surface and applied
as the biorecognition
element for the
detection of analyte.
AFM1 Aspergillus/ SPCE MoS2 On the surface Antibody-based CV/EIS Milk 0.2–10 ng 0.06 ng [66]
Aspergillus QDs@UiO-66- of the working biosensor: the mL− 1 mL− 1
flavus/ NH2 electrode surface of SPE was
Aspergillus -nanocomposite modified with
parasiticus/ nanomaterial (s) and
Aspergillus then the antibody
nomius was immobilized on
the surface and
applied as the
biorecognition
element for the
detection of analyte.
(continued on next page)

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M. Negahdary et al. Microchemical Journal 185 (2023) 108281

Table 1 (continued )
Analyte Analyte origin Type of Nanomaterial Nanomaterial Electrode Detection Application Detection LOD Ref.
SPE (s) (s) position (s) configuration technique to samples range

AFB1 Aspergillus SPE- Nano CB/ In a conjugated Antibody-based CA Corn 33–1557 13 pg [68]
flavus/ graphite Magnetic beads form with the biosensor: the pg mL− 1 mL− 1
Aspergillus biosensing surface of SPE was
parasiticus platform treated with
antibodies
containing magnetic
beads and HRP
enzyme which
applied as the
biorecognition
element for the
detection of analyte.
AFB1 Aspergillus SPE AuNPs/GQDs On the surface Chemical sensing LSV Malted 1–50 nM 0.47 nM [71]
flavus/ of the working platform barley
Aspergillus electrode
parasiticus
DON)/3- Fungus SPCE Carbon Carbon 3D printed EIS Apoptotic DON: DON: [55]
ADON)/ Fusarium nanofiber/ nanofiber: In a electrochemical cell- cells/ 0.1–10 μg 0.07 μg
15- graminearum AuNPs conjugated based biosensor: the Necrotic mL− 1/3- mL− 1/3-
ADON form with the surface of the signal cells ADON: ADON:
biosensing transducer was 0.05–100 0.10 μg
platform/ modified with AuNPs μg mL− 1/ mL− 1/15-
AuNPs: On the through an 15-ADON: ADON:
surface of the electrodeposition 0.1–10 μg 0.06 μg
working method; then, a mL− 1 mL− 1
electrode mixture contains
cancer cells, a
hydrogel, and carbon
nanofiber in a
conjugated form was
added and the assay
was shadowed
electrochemically.
Glycoside Solanum genus Polyester GO/AuNPs On the surface Chemical sensing DPV — 10–1000 3.4 μM [72]
Toxins plants SPE of the working platform μM
electrode

* Application to real samples not reported; CA: Chronoamperometry; UCNPs: Upconversion nanophosphors; PEC: Photoelectrochemical; DPV: Differential pulse
voltammetry; AIdnb: anti-idiotype nanobodies; CV: Cyclic voltammetry; GQDs: Graphene QDs; LSV: Linear sweep voltammetry; GO: Graphene oxide.

Fig. 5. Schematic presentation related to an electrochemical sensing platform to determine various concentrations of Pb2+ using a modified SPCE with PDA-PPy;
License Number 5386160387445.

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M. Negahdary et al.
square wave voltammetry (SWV), signal-on) at trace level in water
samples. The proposed sensor showed a wide linear detection range, and
LOD for Hg2+ and Cr6+ was 1 ppb and 20 ppb, respectively. The stability
performance of this sensor was reported over 30 days, and the desired
reproducibility and selectivity were attained. The selectivity test with a
tenfold excess of other metal ions demonstrated that responses remained
with insignificant change in the presence of all metal ions. Additionally,
the sensor displayed suitable recovery values in tap and tannery water
samples.
In another research, a multiplexed sensing platform was developed
using a SPCE modified with graphene/amino‑functionalized metal-
organic framework (MOF) to determine Cd2+, Pb2+, Cu2+, and Hg2+
[81]. Here, UiO-66-NH2 was prepared by adding aminoterephthalic acid
and zirconium chloride in a DMF solution containing acetic acid. Af­
terward, the 3DGO-UiO-66-NH2 nanocomposite was achieved by mixing
the required components. Transmission electron microscopy (TEM)
analysis showed an average size of about 50–60 nm and an octahedral
structure for UiO-66-NH2 nanocomposite, and the successful attachment
of the nanocomposite on the 3DGO surface was confirmed. Subse­
quently, the modified form of the electrode (SPCE/3DGO-UiO-66-NH2)
was obtained by drop casting of the nanocomposite on the surface of
SPCE. Then the electrochemical performance of the modified electrode
was evaluated by CV in the presence of Fe(CN)3− 6
/4−
as the redox
marker. The results showed a higher conductivity for the modified
electrode with the nanocomposite. The designed sensor could simulta­
neously detect four toxic metal ions (Cd2+, Pb2+, Cu2+, and Hg2+) by
DPV measurements. For all analytes, the linear range (signal-on
behavior) was from 0.01 to 0.35 pmol/L, and the reported LOD was 3.1
fmol L− 1, 5.98 fmol L− 1, 2.89 fmol L− 1, and 10.9 fmol L− 1 for Hg2+,
Pb2+, Cu2+ and, Cd2+, respectively.
Mercury is one of the most toxic heavy metals, and if used improp­
erly, it can pollute ecosystems and the environment by entering the
nutritional cycle. In addition, releasing this substance into the atmo­
sphere is dangerous and has a very high and long-term toxicity in human
fat tissue [82,83]. In a study, a sensor was developed based on a
modified SPCE with AuNPs for monitoring gaseous elemental mercury
(Hg(0)) [84]. Here, for the detection of mercury, a system was designed
to generate gaseous elemental mercury equipped with a ventilation
system that allowed the passage of air containing mercury vapor on the
surface of a modified SPCE with AuNPs. After this step, a drop of HCl
was pipetted onto the electrode’s surface, so the amalgamated Hg(0)
atoms were stripped as Hg2+ in the solution. The analyte detection
process was performed through the SWASV technique, and the vol­
tammetric response showed defined peaks associated with Hg redox
processes. In this sensing platform, two exposure times were studied (10
and 180 min), and the linear detection ranges were found to be from
5.88 to 56.39 ng dm− 3 with LOD about 2.41 ng dm− 3 and from 0.23 to
5.69 ng dm− 3 with LOD about 0.24 ng dm− 3, respectively.
Sulfite (O3S− 2) is one of the most common chemical additives used in
food to inhibit microbial reactions. However, ingesting O3S− 2 doses
above the permitted levels can cause organoleptic changes and asthma
in humans [85]. In a recent study, a nanocomposite of Ce3+-doped CuO
was used to build an electrochemical sensor to determine O3S− 2 in water
and soft drinks [86]. The physical adsorption procedure was used to
modify SPE with Ce3+-doped CuO, while dropwise addition of Ce3+-
doped CuO solution was performed for the surface of the working
electrode. The prepared electrode was used for O3S− 2 detection based on
its oxidation peak. The O3S− 2 oxidation peak (DPV) increased along
with the concentration increment (signal-on). This linear relationship
was obtained for a linear set of concentration ranges from 0.6 to 400
µmol/L, and the LOD was 0.08 µmol/L. In addition, the results of this
work showed that the developed electrode has adequate characteristics
for determining O3S− 2 in real water and soft drinks samples.
The presence of nitrite (NO−2 ) in the human body can limit oxygen
transport to the blood through the oxidation of hemoglobin to methe­
moglobin. Based on a SPCE modified with AuNPs-poly(ethyleneimine)
8
Microchemical Journal 185 (2023) 108281
nanomaterial, the development of an electrochemical sensor for NO−2
detection was shadowed [87]. The AuNPs-polyethyleneimine was syn­
thesized from a mixture of the metallic hammer solution of HAuCl4 and
the poly(ethyleneimine). Subsequently, a SPCE electrode was modified
with synthesized AuNPs- poly(ethyleneimine), presenting an electro­
chemically active area 1.57 times greater than the bare SPCE electrode.
Electrochemical assays for NO−2 detection were performed by DPV,
confirming a linear detection range (signal-on behavior) from 0.01 to 4
µmol/L and with a LOD of 2.5 nmol/L.
Table 2 presents the most important features of electrochemical
sensors designed to detect inorganic species. This table includes the
latest research based on SPEs as the signal transducer.
4. Electrochemical (bio)sensors developed for the detection of
pesticides and other organic residues
4-aminophenol is a toxic compound used as raw material to produce
paracetamol. This toxic agent can lead to eczema, teratogenicity, and
skin irritations. Recently, a sensing platform was developed to detect 4-
aminophenol using a modified SPCE with the Co3O4@g-C3N4 nano­
composite [106]. Initially, the g-C3N4 was prepared by heat treatment to
improve the conductivity of Co3O4 in a nanocomposite form synthesized
through a hydrothermal method. The investigation of the functional
groups in the nanocomposite was followed by the FT-IR analysis, and the
results were compared with the g-C3N4. For the nanocomposite form,
two peaks were found at 491 and 662 cm− 1, assigned to Co3+ and Co2+
stretching vibrations that confirmed the Co3O4 was incorporated into
the graphite carbon nitride structure. Subsequently, the SPE was
modified with Co3O4@g-C3N4 nanocomposite by drop-casting. The
electroactive surface area of the SPE/Co3O4@g-C3N4 was about 4.8
times enhanced compared to the bare SPE. The electrochemical evalu­
ation of 4-aminophenol was accompanied by the DPV analysis in a PBS
buffer as the electrolyte. The electro-oxidation mechanism of P-amino­
phenol involves two electrons and two protons exchanging with a
reversible redox behavior. According to electrochemical evaluation, an
enhancement in the anodic peak current occurred along with increasing
amounts of the analyte (signal-on behavior). The developed sensor could
detect the analyte in a linear range from 0.05 to 780 µmol/L, and the
found LOD was about 0.015 µmol/L.
4-nitrophenol (4-NP) is a hazardous chemical used to produce pes­
ticides, pharmaceuticals, and explosives whose improper disposal con­
taminates natural sources, making it harmful to humans and animals. A
material used widely for electrode modification is the MOFs which are
crystalline materials built up by the coordination of metal ions and
organic ligands, own an ultra-high and ordered porosity, huge surface
area (up to 10,000 m2/g surface area of Langmuir), and also desired
chemical and thermal resistances [107,108]. Copper MOF (Cu-MOF) is
often used for sensing missions due to its electrocatalytic properties.
Hence, Ambaye et al., combined Cu-MOF synthesized by a solvothermal
procedure with N-doped graphene oxide (NGO) to get a synergistic role
in improving electron transference between electrode/electrolyte to
detect 4-NP [108]. In this research, the prepared Cu-MOF@NGO nano­
composite was uniformly dispersed on the surface of a SPCE by drop-
casting to expand the electroactive area and improve electron transfer
attained from redox probes such as Fe(CN)3− 6 and ferrocene. The
impedimetric characterization was done considering the modified SPCE
with nanocomposite in a solution containing Fe(CN)3− 6
/4−
redox couple
probe. The results confirmed a significant decrement in the charge
transfer resistance, demonstrating the key application of the mentioned
nanocomposite in improving the electrocatalytic effect. Nevertheless,
the nanocomposite showed a remarkable signal amplification effect,
generating a cathodic peak 3-fold higher than the unmodified SPE and
providing a LOD (0.035 µmol/L) for 4-NP detection. However, the
relative simplicity in electrode fabrication and the Cu-MOF@NGO
nanocomposite synthesis provided a linear detection response
(0.5–100 µmol/L) against the analyte.
M. Negahdary et al. Microchemical Journal 185 (2023) 108281

Table 2
Substantial attributes of electrochemical (bio) sensors involving nanomaterials-based SPEs for the detection of toxic inorganic species.
Analyte Type of Nanomaterial (s) Nanomaterial Electrode Detection Application to Detection LOD Ref.
SPE (s) position (s) configuration technique samples range

Pb2+/Cd2+ SPE Co3O4@graphitic On the surface Chemical sensing DPV Water Sample Pb2+: 0 – Pb2+: 3.2 ppb/ [76]
carbon nanocomposite of the working platform 140 ppb/ Cd2+: 3.5 ppb
electrode Cd2+: 0 –
140 ppb
Pb2+/Cd2+ SPE PM**-g-C3N4 On the surface Chemical sensing DPV River Water/ 0.1–1 µM Pb2+: 0.008 [88]
nanocomposite of the working platform Lake water/ µM/Cd2+: 0.02
electrode Tap Water µM
Pb2+/Cd2+ SPCE 2D β-antimony On the surface Chemical sensing DPASV Tap water Pb2+: Pb2+: 0.3 μg L− 1 [89]
of the working platform 1.1–128.3 Cd2+: 2.7 μg
electrode µg/L/Cd2+: L− 1
9.1–132.7
µg/L
Pb2+/Cu2+ SPCE TC4/AuNPs On the surface Chemical sensing DPV River water 0.2–1 ppm Pb2+: [90]
2
nanocomposite of the working platform 0.7982×10−
electrode ppm/Cu2+:
2
1.3358×10−
ppm
Pb2+ SPCE Bi NPs On the surface Chemical sensing SWASV Tap water 0.5–120 μg 0.02 μg L− 1 [91]
of the working platform L− 1
electrode
Pb2+ SPCE PDA-PPy On the surface Chemical sensing SWASV Tap water/ 3–300 μg L− 1
0.15 μg L− 1
[77]
of the working platform River water
electrode
Hg2+/ SPCE 3DGO-UiO-66-NH2 On the surface Chemical sensing DPV Rice/Milk/ Hg2+: Hg2+: 3.1 fM/ [81]
Pb2+/ nanocomposite of the working platform Honey 0.01–0.35 Pb2+: 5.98 fM/
Cu2+/ electrode pM/Pb2+: Cu2+: 2.89 fM/
Cd2+ 0.01–0.35 Cd2+: 10.9 fM
pM/Cu2+:
0.01–0.35
pM/Cd2+:
0.01–0.35
pM
Zn2+/ SPCE AuNPs/PANI- On the surface Chemical sensing SWASV Water 1–180 μg L− Zn2+: 0.039 μg [92]
Pb2+/ MWCNTs of the working platform 1
L− 1/Pb2+:
Cu2+ electrode 0.037 μg L− 1/
Cu2+: 0.017 μg
L− 1
Cd2+ SPCE CB-AuNPs On the surface Aptamer-based SWV Tap water 1–50 ppb 0.14 ppb [93]
nanocomposite of the working biosensor: the
electrode surface of SPE was
modified with
nanomaterial (s) and
then a thiol-
functionalized
aptamer was
immobilized on the
surface and applied
as the biorecognition
element for the
detection of analyte.
Cd2+/ SPCE rGO/MoS2 composite On the surface Chemical sensing DPV Rice Cd2+: 5–160 Cd2+: 49.8 µM/ [94]
Hg2+/ of the working platform μM/Hg2+: Hg2+: 37 µM/
Pb2+ electrode 5–160 μM/ Pb2+: 734 µM
Pb2+:
10–3000 μM
Hg2+/Cr6+ SPE Thymine-GO- On the surface Chemical sensing SWV Tap water/ 5–600 ppb Hg2+: 1 ppb [80]
carbohydrazide of the working platform Tannery water Cr6+: 20 ppb
nanocomposite electrode
NO3– SPE- Cu nanoclusters On the surface Chemical sensing LSV Tap water/ 0.05–5 mM 0.2 nM [95]
silver of the working platform River water
electrode
NO2– SPCE AuNPs On the surface Chemical sensing DPV —*** 0.01–4 µM 2.5 nM [87]
of the working platform
electrode
As3+ SPCE AuNPs On the surface Chemical sensing SWASV Ground water 3–25 ppb 3 ppb [96]
of the working platform
electrode
As3+ SPCE AuNPs-GO On the surface Aptamer-based DPV Shellfish 4×10− 4 − 2×10− 4
mg L− 1
[97]
nanocomposite of the working biosensor: the 10 mg L− 1
electrode surface of SPE was
modified with
nanomaterial (s) and
then a thiol-
(continued on next page)

9
M. Negahdary et al. Microchemical Journal 185 (2023) 108281

Table 2 (continued )
Analyte Type of Nanomaterial (s) Nanomaterial Electrode Detection Application to Detection LOD Ref.
SPE (s) position (s) configuration technique samples range

functionalized
aptamer was
immobilized on the
surface and applied
as the biorecognition
element for the
detection of analyte.
As3+ SPCE rGO On the surface Chemical sensing DPV Tap water 2–40 nM 2.9 nM [78]
of the working platform
electrode
3
Hg+ SPCE AuNPs On the surface Chemical sensing SWASV — 0.23–56.4 0.23 ng dm− [84]
of the working platform ng dm− 3
electrode
Hg2+ SPE-gold Zn-Ag-In-S QDs On the surface Chemical sensing DPV — 10 pM − 1 0.11 pM [98]
of the working platform μM
electrode
Hg2+ SPCE GO On the surface Aptamer-based DPV Tap water 0.01–300 nM 0.009 nM [99]
of the working biosensor: the
electrode surface of SPE was
modified with
nanomaterial (s) and
then several
methylene blue
labeled aptamers
were immobilized on
the surface and
applied as the
biorecognition
element for the
detection of analyte.
Hg2+ SPCE AgNWs-HPMC* On the surface Enzyme-based CV Commercial 5–25 µM 3.94 µM [100]
nanocomposite of the working biosensor: the Drinking
electrode surface of SPE was Water
modified with
nanomaterial (s) and
then the Urease was
immobilized on the
surface and applied
as the biorecognition
element for the
detection of analyte.
Chromium SPCE Au-Ag nanocomposite On the surface Chemical sensing DPV/SWV Wastewater 0.05–5 ppm 0.1 ppb [101]
(Cr+3)/ of the working platform
(Cr+4) electrode
SO2−
3 SPCE Ce3+-doped CuO On the surface Chemical sensing DPV Non-alcoholic 0.6–400 μM 0.08 μM [86]
nanocomposite of the working platform malt drink/
electrode Orange Juice/
Bottled water/
Tap water
1
Cadmium/ SPE-gold CdTe/CdS QDs On the surface Chemical sensing DPV Tap water 3.1–49.1 μg 2.82 μg L− [102]
Lead nanomaterials of the working platform L− 1
electrode
1 1
Lead SPCE Poly(1,5- On the surface Chemical sensing SWASV Tap water 0.5–5 μg L− 0.3 μg L− [103]
diaminonaphthalene) of the working platform
film nanowire electrode
NO SPCE CeMOF NPs On the surface Chemical sensing Amperometry HeLa and 6–313 μM 2 nM [104]
of the working platform 293A cells
electrode
Hydrazine SPE- 2D MoS2 nanosheets On the surface Chemical sensing CA Tap water/ 3.81–400 μM 1.1 μM [105]
graphene of the working platform River water
electrode

* HPMC: hydroxypropyl methylcellulose; **PM: poly(melamine); *** Real sample application not reported; PDA-PPy: Dopamine polymer doped polypyrrole; PANI-
MWCNTs: polyaniline-multi-walled carbon nanotubes.

In a research, magnetically activated carbon-cobalt (MAC-Co)
nanocomposite was utilized to modify a SPE for electrochemical sensing
toward Bisphenol A [109]. Here, the hybrid nanomaterial provided
catalytic activity in the Bisphenol A detection, incrementing the elec­
trochemical current three times and anticipating the anodic process in
110 mV compared to the bare SPE, which yielded more sensitivity and
selectivity. This behavior was ascribed to the improved surface area and
could create a synergic effect between activated carbon and Co3O4
particles. The authors determined important electrochemical
parameters such as the type of mass transport that was diffusional by the
Randles-Sevcik equation, Bisphenol A diffusional coefficient by the
Cottrell equation (D = 8.6×10− 5 cm2 s − 1), and transfer coefficient by
Tafel plot (α = 0.28). Also, a mechanism has proposed the reaction by
varying medium pH where the oxidation occurred in hydroxyl groups
involving two electrons and two protons. The designed sensor confirmed
reasonable performance, including satisfactory reproducibility, repeat­
ability, and stability for three weeks without significant signal decre­
ment. It exhibited selective performance against a tenfold excess of

10
M. Negahdary et al.
inorganic (i.e., NaCl, KCl, CaCl2, and MgCl2) and organic (i.e., hydro­
quinone and phenol) chemicals. Finally, the sensor was applied to tap,
river, mineral waters, and milk samples; it presented well-recovering
values with minor RSD, showing that the samples’ matrix did not
interfere significantly. The presented sensing platform could detect
Bisphenol A in a linear range from 0.1 to 350 μmol/L, and the found LOD
was 10 nmol/L.
Water pollutants have caused great concern due to their toxic effects.
In a study, a cell-based electrochemical sensor was employed to detect
several contaminants (2,4,6-trichlorophenol, bisphenol AF, and poly­
styrene nanoplastics) in aquatic environments [110]. For fabricating a
modified SPCE with WS2-MWCNTs nanocomposite, purified MWCNTs-
OH was prepared and then mixed with WS2 nanosheets. The resulting
solution was centrifuged to remove unbound WS2 nanosheets. After­
ward, the final product was dropped on the surface of the SPCE and
dried through infrared light to obtain the desired electrode (WS2/
MWCNTs-OH/SPCE). The detection of cytokine-induced killer cells
(CIK) cells was tracked due to the electroactivity of a mixture of
xanthine/guanine in cells. These two compounds showed an anodic
peak in the CV analysis, and the presence of WS2/MWCNTs-OH pro­
moted the electrocatalytic activity of the sensor; it could facilitate the
process of charge transfer on the electrode surface. The linear detection
range found by the mentioned sensor was from 2.0×103 to 6.5×106 cells
mL− 1. The half inhibitory concentration (IC50) values were 169.96
μmol/L, 21.88 μmol/L, and 123.01 μg mL− 1 for 2,4,6-trichlorophenol,
bisphenol AF, and polystyrene nanoplastics, respectively.
Paraoxon is one of the organophosphorus compounds widely
employed as a pesticide and insecticide; however, it can be a toxicant in
the nervous system of living organisms. In a study, BiVO4 nano dendrites
synthesized by a hydrothermal method were utilized to modify the SPCE
for electrocatalytic detection of Paraoxon using DPV [111]. Here, the
signal transducer was equipped with nano dendrites to exploit the fa­
vorite interaction between BiVO4 and Paraoxon, aiming to improve the
electron transfer rate and surface conductivity. The presence of the
nanomaterial provided a high surface area which facilitated reaching a
low LOD and achieving improved sensitivity. The nanomaterials’ speci­
ficity and properties depend on the synthesis composition, homogeneity,
and morphology. The electrochemical assays were performed through
the DPV technique, while two more reversible peaks were found, indi­
cating the conversion of Paraoxon’s reduction product (diethyl(4-
hydroxylaminophenyl) phosphate) to diethyl(4-nitrosophenyl) phos­
phate. The sensor exhibited desirable performance (signal-on) for
detecting Paraoxon in a linear range from 0.2 to 1.96 µmol/L and with a
LOD of about 0.034 µmol/L.
Chlorpyrifos (CPF), one of the most used organophosphate pesti­
cides, has caused huge concern in food safety due to its toxicity.
Recently, the development of an electrochemical aptamer-based
biosensor based on a PET-printed electrode system (SPE-silver) was re­
ported, where silver was the working electrode area [112]. For the
production of the aptasensor, the working electrode area was func­
tionalized with 11-mercaptoundecanoic acid (11-MUA), producing the
Ag electrode modified with a self-assembled monolayer of thiol
(11MUA-Ag). Then, the surface of the working electrode was treated
with EDC/NHS as a cross-linker. Subsequently, an amino-functionalized
aptamer as the biorecognition element was immobilized on the surface
of the electrode via a covalent bond directed by the EDC/NHS between
the amine and carboxyl groups activated on the surface of the working
electrode. Finally, the unwanted aptamer strands on the surface were
blocked by the BSA, and the prepared aptasensing platform was applied
to detect the analyte. In the presence of the analyte, the observed
analytical response showed a decrease in the reduction peak, a direct
relationship with the increment in the analyte concentration (signal-off
behavior). The presented biosensor could detect CPF in a linear range
from 1 to 105 ng mL− 1 with a LOD of 0.097 ng mL− 1.
Paraquat or 1,1-Dimethyl-4,4-bipyridinium dichloride is a popular
herbicide widely used in agriculture worldwide. The highly toxic
11
Microchemical Journal 185 (2023) 108281
amount of this chemical agent can cause several disorders in the respi­
ratory system and several vital organs of individuals and even death. In a
research, to detect paraquat, an electrochemical sensor was fabricated
using a SPE-silver modified with PbO-NPs [113]. For electrode prepa­
ration, a suspension containing PbO-NPs was dropped on the surface of a
SPE. The electrochemical detection of paraquat was followed via the CV
technique, which monitored the interaction of the analyte with the
presented nanocomposite on the electrode surface. The positively
charged paraquat molecule attracted by the negatively charged PbO-NPs
could create an accumulation of paraquat on the electrode surface,
thereby improving the sensitivity and selectivity. The developed sensor
exhibited a linear response ranging from 1 mmol/L to 5 mmol/L and
LOD of 1 mmol/L.
Parabens are chemicals widely used as preservatives in various in­
dustrial products such as food, cosmetics, and pharmaceuticals. In recent
years there has been increased concern about the safety of these com­
pounds due to their endocrine disrupting activity. In a study, disposable
SPCEs were utilized for amperometric detection of parabens in a com­
plex matrix [114]. Here, three SPCE electrodes, including different
working areas (bare carbon, modified with mesoporous carbon, and
modified with graphene), were employed as the signal transducer. The
electrode was connected to a flow injection analysis system and coupled
with high-performance liquid chromatography (HPLC). The linear range
was from 0.010 to 30 mg L− 1 with a LOD of 20 μg L− 1. The proposed
sensing platform has been applied to determine the toxicity of different
parabens in samples of shampoos, body creams, facial tonics, and kinds
of toothpaste.
Hydroquinone is a product widely used in the pharmaceutical, dyes,
plastics, pesticides, paper, and cellulose industries which is often dis­
carded as industrial waste [115]. This chemical is classified as corrosive;
it can pose a severe risk to human health and the environment. Health
risks include skin irritation and other dermatological conditions, allergy,
eye injuries, gastrointestinal symptoms, and DNA damage. In a research,
hydroquinone was detected in tap water using a flexible photo­
electrochemical sensor modified with carbon spherical shells [116]. For
building the sensor, a SPCE was produced from a polyester stencil and
the carbon conductive ink on the surface of the polyester substrate using
a polyurethane squeegee. A pretreatment step was carried out for the
achieved SPCE in a solution of H2SO4, using the CV to remove non-
conductive compounds and impurities from the carbon ink. After this
step, the surface of the electrode was modified with carbon spherical
shells that were pipetted onto the surface. The detection system con­
sisted of a working electrode illuminated by a light source and
controlled by a circuit board connected to a computer. When the sensor
was exposed to light, carbon spherical shells (a photoactive material),
and excited electrons, in this process, the oxidation of hydroquinone
happened, and the photocurrent response was recorded as a detection
response. The linear detection range was from 3 to 23 μmol L–1, with a
LOD of 2.7 μmol L–1.
Chlorpyrifos is an organophosphate (O, O-diethyl-O-(3,5,6-tri­
chloropyridin-2-yl) phosphorothioate), a widely synthetic insecticide
used and has a neurotoxic effect in humans. Residues of this pesticide are
found in food and water sources. In a study, a system for nonenzymatic
electrochemical sensing of organophosphate pesticide was constructed
by SPEs modified with bimetallic Mn-Fe MOF nanocomposite [117]. The
synthesized MOF was added to a mixture of 2-propanol and Nafion
polymer solution to modify the electrode surface. Then, this mixture was
drop-casted on the surface of the signal transducer. Different concen­
trations of chlorpyrifos were added and analyzed by the SWV technique.
This sensing platform could detect the analyte in a linear range from
1×10− 9 mol L− 1 to 1×10− 7 mol L− 1, and the determined LOD was 0.852
nmol/L. The developed sensor could detect chlorpyrifos in ultra-trace
concentrations and showed the desired selectivity for several
interferences.
Metal oxides have attractive features, including great catalytic ac­
tivity, high specific surface area, chemical stability, and the ability to
M. Negahdary et al.
form different nanostructures [118,119]. TiO2 NPs are an n-type metal
oxide semiconductor material with a broad energy band gap (low-con­
ductivity) [119]. Hence, endeavors have been achieved to alter TiO2 ­
nanostructures or modify them to increase charge mobility and change
energy band structure for better employment in sensing and catalytic
purposes [119,120]. In a research, a microstructured composite
comprised of TiO2 and a semiconducting material poly(triazine imide)
(PTI)-an allotrope of carbon nitride (synthesized by the hydrothermal
method) was used for simultaneous detection of fipronil (FIP) and its
toxic metabolite fipronil sulfone (FIP-S) in egg and water samples [121].
An adequate amount of the mentioned composite was dripped on a SPE
surface to perform the physical modification. The resulting material
exhibited good homogeneity with small particles organized hierar­
chically, facilitating electron diffusion and providing excellent sensi­
tivity in the oxidation of FIP and FIP-S. The EIS and SWV evidenced the
electron transfer improvement where the charge transfer resistance in Fe
(CN)3–/4–
6 solution decreased. FIP peak potential shifted slightly to a
lower value, and the SWV current increased (signal-on). The sensor
presented stability over a month and enough selectivity against the 10-
fold excess of similar inorganic compounds. Also, the sensing perfor­
mance showed reliable results in the real egg and water samples. The
presented sensor could detect analytes in a linear range from 0.01 to 10
μmol/L (LOD: 8.42 nmol/L) and 10 to 50 μmol/L (LOD: 9.72 nmol/L) for
FIP and FIP-S, respectively.
Palladium nanoparticles (PdNPs) have superb catalytic, conductiv­
ity, and electrochemical properties. They are plentiful and inexpensive
and, when linked to Pt and Au, make one of the most applied materials
[122–124]. By precipitating PdNPs or Pd nanocomposites to incorporate
with MIP, the hybrid materials that enable high analyte affinity and
selective detections can be obtained. MIPs capture analytes by the
complementary cavities in size, shape, and spatial pattern, and the usage
of nanoparticles allows them to enhance their binding capacity due to a
higher surface area-to-volume ratio, improves binding kinetics, and the
active surface area accessibility [123,125]. In a research, Somnet et al.
used PdNPs@MIP to modify graphene-ink SPE (SPE-graphene) fabri­
cated on polyvinyl chloride sheets for selective and sensitive detection of
N-Nitrosodiphenylamine (NDPhA) in beverage samples [123]. NDPhA is
a mutagenic and carcinogenic chemical broadly existing in beverages,
cosmetics, processed foods, and cigarettes that can potentially contam­
inate even public water systems [123]. Here, the MIP was prepared
through a precipitation method on the poly(vinylpyrrolidone)-coated
PdNPs in the presence of N-isopropylacrylamide (as a monomer),
NDPhA (as a template), trimethylolpropane trimethacrylate (as a cross-
linker), and 2,20-azobis(2-methylpropionitrile) (as the initiator). To
make assays, the employed electrolyte with pH = 3 provided the wanted
interaction for monitoring NDPhA. Also, the proposed mechanism for
the oxidation process related to the nitroso group contained one electron
and one hydrogen, which was determined by the Nerst theory. The
Laviron equation determined a five-time greater reaction standard rate
constant using PdNPs@MIP/SPE-graphene (593.69 s− 1) than SPE-
graphene (128.63 s− 1), showing the efficiency of the proposed sensor
in oxidizing of NDPhA. It exhibited wanted selectivity through two ex­
periments employing commonly organic and inorganic compounds in
beverages. In addition, the designed sensor showed the desired repro­
ducibility and 28 days of stability. The presented sensing platform could
detect the analyte in a linear range from 0.01 to 100 μmol/L with a LOD
of 0.0013 μmol/L.
While MnO2 has poor conductivity, it can possess prominent elec­
trochemical activity, anticipates overpotential preventing interferences
from other compounds, and yields fast electron transfer affording
attractive features for electrochemical sensors. Hence, its composite
with a highly conductive material (graphene nanoplatelets (GNPs)) al­
lows for individual, or simultaneous detection of broadly used carba­
mate pesticides (i.e., carbaryl (CBR), fenobucarb (FNB), and carbosulfan
(CBS)) was introduced in an electrochemical sensing platform [126]. By
combining both materials, they acted synergically to improve catalytic
12
Microchemical Journal 185 (2023) 108281
traits; lading MnO2 on the GNPs avoided the aggregation resulting from
π-π stacking between graphene sheets which impaired conductivity and
decreased the MnO2 electrical resistance. The achieved nanocomposite
was used to modify a SPCE prepared on a transparency paper. A
remarkable anodic peak with overpotential anticipation and an increase
in current was observed in detecting these three carbamates in their
phenolic forms. This electrocatalytic effect was ascribed to a mechanism
where MnO2 participates, reducing to Mn2O3 or MnO to form a carba­
mate’s dihydroxy intermediate; subsequently, the intermediate loses
two electrons and two protons to result in the o-benzoquinone final
product. In contrast, Mn oxides ended up re-oxidizing to MnO2, recon­
stituting themselves. The proposed sensor provided carbamate nonen­
zymatic detection. Therefore, problems related to enzymatic reaction-
based biosensors, including detection of the analyte through enzyme
inhibition, high price, and its sensitivity to pH, temperature, moisture,
and chemicals, have been circumvented. Plus, since the device was
disposable, electrode fouling caused by phenol has been evaded. The
proposed sensor showed a wide linear response, and the LOD for CBR,
FNB, and CBS was found to be about 0.30, 1.30, and 14.90 μmol/L,
respectively.
Table 3 presents the most important features of electrochemical
sensors designed to detect pesticides and other organic residues. This
table includes the latest research based on SPEs as the signal transducer.
5. Electrochemical (bio) sensors involving nanomaterials-based
SPEs for the detection of drugs
The unwanted doses of methotrexate as an anticancer drug will
create toxic effects on normal cells. In a research, a methotrexate elec­
trochemical sensing platform was developed based on a modified
screen-printed graphite electrode (SPGE) with Fe3O4-polypyrrole (ppy)-
Pd nanocomposite as the signal transducer [147]. In order to produce
the nanocomposite, Fe3O4 NPs were synthesized, and then, in the
presence of pyrrole and palladium (II) acetate, the nanocomposite was
achieved. Afterward, the SPGE was modified with the mentioned
nanocomposite that improved the electrochemically active surface area
by enhancing 4.2 times compared to the bare SPGE. The electrochemical
assay of methotrexate was followed by DPV in an electrolyte containing
PBS buffer. Here, by increasing the analyte concentration, the anodic
currents increased represented a signal-on behavior. This electro­
chemical sensor could detect the methotrexate linearly from 0.03 to 100
μmol/L, and the reported LOD was about 7 nmol/L.
6-mercaptopurine (6-MP) is a drug used as an anti-inflammatory and
anticancer agent, and exceeding levels of it will lead to some health
problems. Therefore, monitoring the low concentrations of this drug
through electroanalytical techniques will help prevent drug poisoning.
In a research, an electrochemical platform was designed to detect 6-MP
using a modified screen-printed graphite electrode (SPGE) with rGO-
Cu2O-Fe2O3 nanocomposite [148]. The first part of the nanocomposite
was synthesized from graphite powder (to produce rGO) and mixed in
ethanol. Then, iron(III) nitrate nonahydrate and copper(II) nitrate tri­
hydrate were added to rGO to reach the desired nanocomposite form.
Afterward, the surface of the signal transducer was physically modified
with the mentioned nanocomposite. This modification improved the
surface area of SPGE and enhanced the sensitivity for detecting analytes
through the DPV. Along with enhancing the various concentrations of
the analyte, the DPV peak currents were enhanced regularly and
confirmed a signal-on behavior. The presented electrochemical sensor
detected the analyte in a linear range from 0.05 to 400 μmol/L, while the
determined LOD was equal to 0.03 μmol/L.
Carbendazim is a broad-spectrum fungicide that contaminates water,
soil, and foods when applied improperly. Ingesting it can cause several
human diseases, significantly increasing the probability of cancer. In a
research, the synergic effect of the combination of nano hexagons SnS2-
Sulfur substituted graphitic carbon nitride (SnS2-SGCN) was applied to
produce an electrochemical sensor for the detection of carbendazim in
M. Negahdary et al. Microchemical Journal 185 (2023) 108281

Table 3
Electrochemical (bio)sensors involving nanomaterials-based SPEs for the detection of pesticides and other organic residues.
Analyte Type of Nanomaterial (s) Nanomaterial Electrode Detection Application to Detection LOD Ref.
SPE (s) position (s) configuration technique samples range

Formaldehyde SPCE Ch-ZnO nanocomposite On the surface Chemical DPV Urine 0.001–0.005 6.2 nM [127]
of the working sensing mM
electrode platform
9
Organophosphate SPCE Mn/Fe MOF nanostructures On the surface Chemical SWV Tap water/ 1×10− − 0.85 nM [117]
7
of the working sensing Garden Soil 1×10− M
electrode platform
DPP SPCE Au-NPs-TiO2-MIP On the surface Chemical DPV Urine 0.1–24.3 ng 0.063 ng [128]
nanocomposite of the working sensing mL− 1 mL− 1
electrode platform
4-aminophenol SPGE Co3O4@g-C3N4 On the surface Chemical DPV Tap water/ 0.05–780 µM 0.015 µM [106]
nanocomposite of the working sensing River water
electrode platform
4-NP SPCE Cu-MOF@NGO On the surface Chemical DPV Wastewater 0.5–100 µM 0.035 µM [108]
nanocomposite of the working sensing
electrode platform
2,4,6-trichlorophenol/ SPCE WS2-MWCNTs On the surface Chemical CV Water 2×103 —* [110]
Bisphenol AF/ nanocomposite of the working sensing samples –6.5×106 cells
Polystyrene electrode platform mL− 1
Nanoplastics
Sudan I SPCE Ni-ZIF-67 nanocomposite On the surface Chemical DPV Tomato 0.03–535 μM 9 nM [129]
of the working sensing paste/
electrode platform Ketchup
sauce/Chilli
powder/Tap
water
Sudan SPCE MnO2 nanorods On the surface Chemical LSV/DPV Tomato 0.25–300 µM 0.08 µM [130]
of the working sensing paste/
electrode platform Ketchup sauce
Paraquat SPE PbO-NPs On the surface Chemical CV Juice/Milk 1–5 mM 1 mM [113]
of the working sensing
electrode platform
1
Parabens SPCE Ordered Mesoporous Carbon/ On the surface Chemical Amperometry Facial Tonic/ 0.01–30 mg 20 μg L− [114]
graphene/carbon of the working sensing Shampoo/ L− 1
nanomaterials electrode platform Body Cream/
Toothpaste
1
4-ethyphenol SPCE AuNPs/fullerene On the surface Chemical DPV Wine 3–25 mg L− 400 μg [131]
of the working sensing L− 1
electrode platform
Hydroquinone SPCE CSS nanomaterial On the surface Chemical PEC Tap water 3–23 μM 2.7 µM [116]
of the working sensing
electrode platform
SDS SPCE ZnO NPs On the surface Chemical DPV Laundry 0.2883–2.883 0.65 mM [132]
of the working sensing wastewater/ mg mL− 1
electrode platform Shampoo
Amaranth SPE g-C3N4 nanocomposite On the surface Chemical DPV Orange juice/ 0.08–340 µM 0.02 µM [133]
of the working sensing Tap water
electrode platform
Amaranth SPCE PPy NTs On the surface Chemical LSV Orange juice/ 0.03–290 μM 0.01 μM [134]
of the working sensing Apple juice/
electrode platform Tap water
Wheat Gliadin SPCE FCONp/MWCNT-CDH On the surface Chemical EIS Gluten-free 0.1–0.8 ng 0.036 ng [135]
nanostructures of the working sensing flour/Gluten- mL− 1 mL− 1
electrode platform free cookies
Hydroxylamine SPE Fe3O4 NPs/GO On the surface Chemical DPV Tap water/ 0.05–700 µM 10 nM [136]
of the working sensing River water/
electrode platform Well water
4-Cyanophenol SPCE CeBiVO4-MWCNT On the surface Chemical DPV Urine 0.001–1207 7.3 nM [137]
nanocomposite of the working sensing µM
electrode platform
Paraoxon SPCE BiVO4 nano dendrites On the surface Chemical DPV River water 0.2–1.96 μM 0.034 μM [111]
of the working sensing
electrode platform
Glyphosate SPGE rGO-double-WCNTs- On the surface Chemical SWV River water 0.1–1000 ppb 0.08 ppb [138]
octahedral-Fe3O4-chitosan of the working sensing
nanocomposite electrode platform
MTL SPCE CoMn2O4@rGO On the surface Chemical DPV Lake water 0.01–1377 μM 0.05 μM [139]
nanocomposite of the working sensing
electrode platform
Bisphenol A Paper- CB nano On the surface Chemical SWV River water/ 0.1–50 µM 0.03 µM [140]
based of the working sensing Drinking
SPE electrode platform water
Bisphenol A SPE ZnO-ZnCo2O4 nanocomposite DPV Drinking 0.06–200 µM 0.01 µM [141]
water/River
(continued on next page)

13
M. Negahdary et al. Microchemical Journal 185 (2023) 108281

Table 3 (continued )
Analyte Type of Nanomaterial (s) Nanomaterial Electrode Detection Application to Detection LOD Ref.
SPE (s) position (s) configuration technique samples range

On the surface Chemical water/Bottled

of the working sensing water/Waste
electrode platform water
Bisphenol A SPCE MWCNTs On the surface Chemical LSV Lake water/ 0.2–500 μM 0.013 μM [142]
of the working sensing Tissue
electrode platform
Bisphenol A SPCE Magnetic activated carbon- On the surface Chemical DPV Kohpayeh 0.1–350 μM 10 nM [109]
Cobalt nanocomposite of the working sensing river water/
electrode platform Tap water/
Mineral
water/Milk
Carbendazim SPCE 2D-gC3N4 nanocomposite On the surface Chemical DPV Orange juice/ 0.099–346.9 6 nM [143]
of the working sensing Vegetables μM
electrode platform extract
Glyphosate SPCE Carbon nanodots On the surface Chemical ECL Tea/Soy milk 28.9–200 pg 8.66 pg [144]
of the working sensing mL− 1 mL− 1
electrode platform
Fipronil/Fipronil sulfone SPE TiO2-polytriazine imide On the surface Chemical SWV Chicken eggs Fipronil: Fipronil: [121]
nanocomposite of the working sensing Water 0.01–10 μM 8.42 nM
electrode platform Fipronil Fipronil
sulfone: 10–50 sulfone:
μM 9.72 nM
Diazinon SPE- Polycaprolactone-chitosan On the surface Chemical DPV Tomato juice 3–100 nM 2.88 nM [145]
MWCNT nanofiber nanofiber of the working sensing
electrode platform
Allura red SPE Nanodiamond@SiO2@TiO2 On the surface Chemical DPV Soft drink/ 0.01–8.65 μM 1.22 nM [146]
nanocomposite of the working sensing Food powder/
electrode platform Orange juice/
Candy/Water
N-nitrosodiphenylamine SPE- PdNPs@MIP nanocomposite On the surface Chemical LSASV Beverages 0.01–100 μM 1.3 nm [123]
graphene of the working sensing
electrode platform
CBR; FNB; CBS SPCE MnO2-graphene On the surface Chemical DPV Jasmine rice/ Individual CBR: 0.3 [126]
nanoplatelets nanocomposite of the working sensing Rice-field detection: CBR: μM
electrode platform water 1–40 μM FNB: 1.3
FNB: 5–150 μM μM
CBS: 50–600 CBS:
μM 14.9 μM
CBR: 1–30 µM CBR: 0.3
FNB: 5–80 µM µM
CBS: 50–400 FNB: 1.4
µM µM
CBS:
15.2 µM

* LOD not reported; DPP: Diphenyl phosphate; 4-NP: 4-nitrophenol; SDS: Sodium Dodecyl Sulfate; MTL: Metol; CBR: Carbaryl; FNB: Fenobucarb; CBS: Carbosulfan; Ch-
ZnO: Chitosan-ZnO; MIP: Molecularly imprinted polymer; CSS: Carbon spherical shells; PPy NTs: Polypyrrole nanotubes; FCONp: Self-assembled flower-like copper
oxide nanoparticles; MWCNT-CDH: Hydrazide-functionalized multiwalled carbon nanotubes; LSASV: Linear sweep anodic stripping voltammetry.

environmental samples [149]. Here, the SnS2-SGCN nanocomposite was
prepared and pipetted onto the surface of a SPCE to improve the
accessible surface area for the detection of the analyte. DPV technique
was used to determine different concentrations of carbendazim. The
results confirmed that the DPV peak current increased in a parallel di­
rection related to enhancing concentrations of the analyte (signal-on).
The linear detection range was from 0.002 to 416 µmol/L, and the LOD
was about 3×10− 8 mol L− 1.
Table 4 presents the most important features of electrochemical
sensors designed to detect drugs. This table includes the latest research
based on SPEs as the signal transducer.
6. Conclusions, outlook and future aspects
Toxic substances, with their destructive effects on the health of
humans, animals, plants, and the environment, lead to death, creating
high treatment costs and environmental cleaning concerns. Toxicity
detection methods of various substances are often expensive, time-
consuming, and have some inaccuracies in the detection process. Elec­
trochemical sensors have been greatly developed in recent years to
improve the early and accurate detection of toxic substances. These
electrochemical platforms have shown several advantages: low cost, fast
design and detection, reproducibility, and enough stability. Equipping
electrochemical sensors with innovative and advanced elements has
improved diagnostic performance. One of the newest signal transducers
recently used in electrochemical sensors is SPEs, whose working elec­
trode surface is made from various materials such as carbon, gold, etc.
These electrodes are widely used due to their miniature structure, high
stability, low cost, flexibility in different conditions, and possibility for
modifications. The special physicochemical properties of different ma­
terials on the nanoscale have created capacities to improve the sensi­
tivity of electrochemical sensors significantly. Usually, these advanced
materials are designed and synthesized in different forms compatible
with the targets. In most cases, they are used to modify the signal
transducer’s surface, which facilitates and increases the electron transfer
between the electrolyte and the accessible surface of the signal trans­
ducer. There are also reports on the use of nanomaterials in other
components of sensors, such as (bio)recognition components, all of
which aim to improve the diagnostic performance of electrochemical
sensors. In recent research, the main nanomaterials used in electro­
chemical sensors to detect toxic substances included gold-based and
carbon-based nanomaterials, which confirmed the biocompatibility,
stability, and proper performance of these nanomaterials in improving
diagnostic performance. The recognition element in these

14
M. Negahdary et al. Microchemical Journal 185 (2023) 108281

electrochemical sensors is equipped with various materials such as an­

[148]

[147]

[150]

[151]

[152]

[153]

[154]

[149]

[155]
tibodies, aptamers, proteins, polymers, enzymes, and other advanced
Ref.
materials to provide more accurate detections, which are used with the
maximum affinity to detect analyte molecules. Recently, there have

nM/6-thioguanine: 6 µM
been reports on designing multiplex electrochemical sensors that

6-mercaptopurine: 10
simultaneously detect several toxic substances, improving diagnostic
mechanisms in monitoring environmental, industrial, and health pol­

DES: 6.5 nM
lutants. It seems a significant gap remained until the commercialization

CAP: 10 nM
7

3×10− 8 M
4.76×10−
of these electrochemical sensors. We recommend that the researchers
0.03 μM

0.13 μM
12 nM
7 nM

6 nM
can make efforts in the subsequent research enabling the knowledge of
LOD

electronics experts to make the necessary systems and circuits to mini­

aturize the electroanalysis, and these electrochemical sensors should not
be necessarily dependent on commercially available potentiostats/gal­

6-mercaptopurine: 0.04–330
μM/6-thioguanine: 1×10− 7
vanostats. Continuous improvement of technical knowledge is not
completely necessary and practical, and the time has come to

CAP: Chloramphenicol; DES: Diethylstilbestrol; MIO@NG: Magnetic iron oxide embed nitrogen-doped graphene; Dy-VO4- f-CNF: Dysprosium vanadate-carbon nanofiber.
CAP: 0.01–200 μM
DES: 0.05–200 μM commercialize these electrochemical sensors, which is a much more
Detection range

0.002–416 μM important goal. In terms of analyte selectivity in the presence of inter­

0.05–400 μM

0.03–100 μM

0.04–195 μM

1.5–1037 µM
3

− 4×10− 4 M
0.4–140 μM
− 10−

fering agents, stability, and repeatability, there are still development

paths with enough space to be reached by upgrading the designs and
6

optimizing the required platforms.

10−

Flagyl tablet/Blood/Urine
Methotrexate tablet/Folic

Fresh milk/Milk powder/

Urine/6-mercaptopurine

Urine/6-mercaptopurine

Declaration of Competing Interest

Application to samples

Doxorubicin injection/

Apple/Orange/Carrot/
Dasatinib tablet/Urine
Tablet/6-thioguanine

tablet/6-thioguanine
acid tablet/Urine

The authors declare that they have no known competing financial

Human Saliva

interests or personal relationships that could have appeared to influence

Fruit juice

Cucumber
Eye drops

the work reported in this paper.

Tablet

tablet

Data availability
Potentiometry

No data was used for the research described in the article.

technique
Detection

Acknowledgments
SWV
DPV

DPV

DPV

DPV

DPV

DPV
LSV

The authors would like to thank the So Paulo Research Foundation-

sensing platform

sensing platform

sensing platform

sensing platform

sensing platform

sensing platform

sensing platform

sensing platform

sensing platform

FAPESP (projects 2019/27021-4, 2017/13137-5, and 2014/50867-3)

configuration

and the National Council for Research-CNPq (processes 311847-2018-

Electrode

Chemical

Chemical

Chemical

Chemical

Chemical

Chemical

Chemical

Chemical

Chemical

8, 465389/2014-7, and 305247/2022-0).

Electrochemical (bio)sensors involving nanomaterials-based SPEs for the detection of drugs.

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