Microchemical Journal 207 (2024) 112086

Contents lists available at ScienceDirect

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

Electrochemical methods for the detection of heavy metal ions: From

sensors to biosensors
Hany Abd El-Raheem a,b, Rabiaa Helim a,c , Rabeay Y.A. Hassan d, Ahmed F.A. Youssef d,
H. Korri-Youssoufi a,* , Charoenkwan Kraiya e,f,**
a
Université Paris-Sacaly, CNRS, Institut de Chimie Moléculaire et des Matériaux d’Orsay (ICMMO), ECBB, 17 avenue des sciences, 91400 Orsay, France
b
Center of Materials Sciences, Zewail City of Science and Technology, October Gardens, 6th of October City, 12578 Giza, Egypt
c
University of Jijel, Laboratory of Applied Energetics and Materials, Jijel, 18000 Ouled Aissa, Algeria
d
Biosensors Research Lab, Zewail City of Science and Technology, 6th October City, Giza, 12578, Egypt
e
Department of Chemistry, Faculty of Science, Chulalongkorn University, Phayathai Road, Pathumwan, Bangkok 10330, Thailand
f
Electrochemistry and Optical Spectroscopy Center of Excellence, Department of Chemistry, Faculty of Science, Chulalongkorn University, Phayathai Road, Pathumwan,
Bangkok 10330, Thailand

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

Keywords: Naturally occurring heavy metals (HMs) present a serious risk to human health and the environment because of
Heavy metal ions their toxicity, persistence, and tendency to bioaccumulate. Their presence in air, water, soil, and food can lead to
Electrochemical voltammetric techniques a multitude of adverse effects, from acute poisoning to chronic health problems. The rapid expansion of
Nanomaterials
industrialization and technology has increased HMs contamination from industrial emissions, mining, agricul-
Aptamers
Modified electrode
ture, urbanization, and e-waste, posing serious risks to ecosystems and public health. To tackle this increasing
challenge, it is essential to develop highly robust, sensitive, and selective electrochemical detection methods for
the rapid identification of heavy metal ions (HMIs) contaminants. This review investigates a variety of elec-
trochemical sensors and biosensors utilizing voltammetric techniques for HMIs detection. It covers voltammetric
methods such as cyclic voltammetry (CV), square wave voltammetry (SWV), differential-pulse voltammetry
(DPV), normal pulse voltammetry (NPV), staircase voltammetry (SV), linear sweep voltammetry (LSV), hydro-
dynamic voltammetry (HV), anodic stripping voltammetry (ASV), cathodic stripping voltammetry (CSV), and
adsorptive stripping voltammetry (AdSV). The review also emphasizes recent advancements in the electro-
chemical detection of HMIs through various sensor and biosensor platforms, including different nanomaterials
and DNA aptamers. These innovations have potential applications in environmental monitoring, food and water
safety, industrial waste management, and public health protection, making them vital tools for safeguarding
human health and the environment from HMIs contamination.

1. Introduction which are poisonous even at low concentrations [3,4]. HMs can be
broadly categorized as essential and nonessential. Essential HMs are
The concept of “heavy metals” is somewhat problematic, as there are necessary for fundamental biological functions in living organisms, such
no widely agreed-upon criteria or authoritative organizations, such as as growth, metabolism, and organ development [5]. Plants, for example,
the International Union of Pure and Applied Chemistry (IUPAC), for its require essential HMs like Zinc (Zn), Iron (Fe), Cobalt (Co), Copper (Cu),
definition. In 1936, Niels Bjerrum initially introduced the terminology Manganese (Mn), and Nickel (Ni), which serve as cofactors vital for the
“heavy metals” in his publication “Inorganic Chemistry” specifying them structure and function of enzymes and other proteins. These essential
as metals with a density exceeding 7 g/cm3 [1,2]. Over the years, elements are typically required in trace amounts, around 10–15 ppm,
numerous authors have altered this term, contributing to its lack of and are known as micronutrients. In contrast, nonessential HMs like
consistency. The most common definition of HMs is that they are metals Lead (Pb), Cadmium (Cd), Mercury (Hg), Chromium (Cr), and Arsenic
with relatively high densities, atomic numbers, or atomic weights, (As) are extremely toxic and have no role in plant metabolic processes,

* Corresponding author.
** Corresponding author at: Department of Chemistry, Faculty of Science, Chulalongkorn University, Phayathai Road, Pathumwan, Bangkok 10330, Thailand.
E-mail addresses: [email protected] (H. Korri-Youssoufi), [email protected] (C. Kraiya).

https://doi.org/10.1016/j.microc.2024.112086
Received 5 October 2024; Received in revised form 29 October 2024; Accepted 31 October 2024
Available online 13 November 2024
0026-265X/© 2024 Elsevier B.V. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
H. Abd El-Raheem et al. Microchemical Journal 207 (2024) 112086

even in trace quantities. The rapid rise in toxic HMs, such as Cd, Pb, and (WHO) are actively involved in this effort [23]. They have established
Hg, is now a major global environmental concern. These metals accu- allowable limits for the concentrations of these substances in water,
mulate in soils due to agricultural practices, mining, and industrial ac- following environmental quality standards (EQS). For example, Table S2
tivities, persisting for extended periods [6]. This reduces soil fertility, summarizes the concentration of metal ions allowed by WHO, EPA, and
degrades soil quality, and inhibits plant growth. Additionally, improper the Occupational Safety and Health Administration (OSHA) regarding
waste disposal, mining runoff, and industrial effluent introduce HMs their toxicity [24]. Therefore, the rapid and sensitive detection of HMIs
into water, harming aquatic life, disrupting ecosystems, and leading to in environmental and food samples, along with quantifying their con-
mercury biomagnification in the food chain [7]. HMs have diverse centrations is paramount.
chemical and physical properties, and they are commonly utilized in
various industries, such as machines, electronics, and high-tech appli- 3. Various analytical techniques used for detecting HMIs
cations. Additionally, they can be found in everyday objects and are
even used in biological and agricultural settings. Unfortunately, due to Currently, several traditional detection methods are utilized for
anthropogenic causes, HMs can enter the water and food chains, posing identifying trace HMIs at low concentrations, including inductively
a risk to both humans and animals [8]. coupled plasma atomic emission spectrometry (ICP-AES) [25], capillary
The main sources of contamination with HMs include natural sources electrophoresis (CE), X-ray fluorescence spectroscopy (XFS) [26],
such as soil, rocks, and HMs ores, industrial sources such as factories of atomic absorption spectroscopy (AAS) [27], ion chromatography with
batteries, metal fabrication, corrugated iron, sheets, cosmetics, paints, ultraviolet–visible spectroscopy (IC-UV–vis) [28], total reflection X-ray
soaps, pharmaceuticals, tanneries, and breweries. Mining activities also fluorescence (TXRF) [29], inductively coupled plasma-mass spectros-
contribute significantly to HMs contamination of the environment; some copy (ICP-MS) [30], neutron activation analysis (NAA) [31], and mi-
residual metals are transported through wind and floods, creating croprobes. Despite their advantages in sensitivity and selectivity for
various environmental problems [9]. In fertilizer sources, some traces of detecting HMI concentrations in diverse environmental and biological
Pb and Cd may enter the soil as contaminants in fertilizers [10]. Phos- samples, these techniques have limitations. These limitations include
phorus fertilizers are sources of HMs in agricultural systems [11]. For complex sample preparation and pre-treatment procedures, lengthy
instance, triple superphosphate may cause an accumulation of the ele- detection times, and the inability to analyze intricate samples [32].
ments Cu, Zn, Pb, and As, as well as an increase in the contamination Additionally, they often require skilled technicians, expensive equip-
potential of these elements, particularly Cd, in the soil. As per the ment, and are restricted to laboratory settings due to their bulky size,
findings of the 5th China Total Diet Study, the prime dietary sources of hindering field and real-time applications [33,34]. Consequently,
Cr, As, Cd, and Al are vegetables and cereals. The primary dietary source considerable efforts have been made in recent decades to address these
of mercury is aquatic items, whereas the main sources of Pb exposure in limitations.
the diet include water, vegetables, beverages, cereals, and meats Unlike the previously mentioned methods for detecting HMIs, elec-
[12,13]. Furthermore, HMs contamination can be found in various trochemical techniques provide a promising option for detecting HMIs
stages of food production, including raw material production, process- due to their inherent advantages, including straightforward equipment,
ing, storage, and transportation [14]. Most HMs are considered low costs, rapid analysis speed, and reliability [35,36]. Additionally,
poisonous substances and are on a high-priority list by the US Envi- electrochemical detection can provide portability and rapid response for
ronmental Protection Agency and the Agency for Toxic Substances and on-site analysis [37,38]. The development of sensitive and selective
Disease Registry [15,16]. This review discusses recent developments in detection methods enables early intervention, thereby mitigating po-
electrochemical sensors for detecting HMs, with a primary focus on the tential long-term effects, such as neurological damage. Accurate meth-
research progress of various electrochemical sensors and biosensors odologies are essential for the analysis of HMIs in complex matrices to
using voltammetric techniques for metal ion detection. Additionally, it minimize the occurrence of false results [39]. Electrochemical tech-
explores the applications of modified electrodes with specific materials niques offer the advantage of real-time monitoring in dynamic envi-
such as metal nanoparticles, carbon nanomaterials, and aptamers. ronments, thereby facilitating regulatory compliance through precise
measurement of HMI concentrations [40,41]. Electroanalytical tech-
2. The Negative impact of toxic HMs on human health niques are increasingly utilized across various applications following the
development of more sensitive pulse methods [42,43]. These methods
Health concerns associated with HMs contaminants arise from their rely on essential electrochemical signals, including potential, charge,
toxicity at high concentrations, leading to detrimental effects on the and current modifications, which serve as analytical signals [44–46].
human body. These include damage and dysfunction in vital organs such Measurement of potential, charge, or current is employed in electro-
as the kidneys, lungs, liver, brain, and blood. For example, Cd can cause chemical characterization to evaluate an analyte’s concentration or
kidney damage and bone demineralization, while Hg and Pb can impair chemical reactivity, making these signals central to all electrochemical
liver and kidney function. Contaminated water often contains carcino- characterization approaches. To detect HMIs, these electrochemical
gens linked to skin lesions and cancers of the skin, lungs, and bladder techniques utilize a system consisting of three electrodes, a reference
[17,18]. Notably, Hg, Pb, Cr, and selenium (Se) pose significant threats electrode (RE), a working electrode (WE), and a counter or auxiliary
due to their high toxicity [19]. These HMIs can deplete essential cellular electrode (CE) [47,48]. The reference electrode is used to measure the
antioxidants by reacting with sulfhydryl (SH) groups in enzymes and potential of the working electrode and maintains a constant electro-
antioxidant molecules. This disrupts cellular energy production, enzyme chemical potential without conducting current. Common reference
function, and antioxidant metabolism, ultimately leading to oxidative electrodes include the silver/silver chloride (Ag/AgCl) and calomel
stress [20]. The increased generation of reactive oxygen species (ROS) (Hg2Cl2/Hg) electrodes. The working electrode, typically made of
overwhelms the body’s natural antioxidant defenses, promoting oxida- “inert” materials such as platinum, gold, or glassy carbon, provides the
tive stress and the development of various diseases and abnormal con- surface for the electrochemical reaction to occur. The counter-electrode
ditions. Metals and their health effects on the human body are given in completes the cell circuit and is generally an inert conductor like
Table S1. graphite or platinum. These three electrodes are immersed in an elec-
Monitoring priority substances and estimating their toxicity is trolyte (an electrically conductive solution) [49,50]. The working elec-
crucial. International agencies such as the Joint Food and Agricultural trode can have various shapes, such as ships, circular, or interdigitated
Organization (FAO), the Center for Disease Control (CDC) [21], the In- configurations. Based on the signal monitored, various electrochemical
ternational Agency for Research on Cancer (IARC) [22], the US Envi- techniques employed to detect HMIs include amperometry, potentiom-
ronmental Protection Agency (EPA), and the World Health Organization etry, voltammetry, impedimetric, and conductometry [51,52]. In

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H. Abd El-Raheem et al. Microchemical Journal 207 (2024) 112086

Table 1
Summarizes examples of electrochemical sensors reported in relation to Voltammetric techniques for electrochemical detection of HMIs.
Sensing Platform Technique Analyte Sensing range Detection limit Ref.
3+
PtNPs@GO/UiO-67 SWSV As 2.7–40 nM 0.42 nM [138]
Pt NPs/PU CV Cu2+ 100–1000 ng/L 16.72 ng/mL [61]
IP6-MWCNTs-ITO DNPASV Cu2+ 1.0 × 10− 8–1.0 × 10− 6
mol/L 2.50 × 10− 9 mol/L [71]
Pt/g-C3N4/PTh NCs DPV Hg2+ 1–500 nM 0.009 nM [139]
L-Au-MOF-GO/GCE DPV Cd2+ 21.9 μg/L 80–560 μg/L [140]
Pb2+ 16.4 μg/L
AuNPs on carbon thread DPV Cd2+ 10–110 μM 1.126 μM [141]
Pb2+ 1.419 μM
Cu2+ 0.966 μM
Hg2+ 0.736 μM
AuNPs LSV Cr6+ 20.0–200.0 μg/L 5.4 μg/L [99]
Au NPs/PUU CV Hg2+ 5–155 ng/mL 0.235 ng/mL [100]
AgNPs/CT/GCE DPASV As3+ 10–100 ppb 1.20 ppb [104]
Sparked SnNP/SPE SWV Cd2+ 1–30 μg/L 0.5 μg/L [106]
Sparked SnNP/SPE SWV Zn2+ 1–30 μg/L 0.3 μg/L [106]
Pd1.5/PAC-900 DPV Cd2+ 0.5–5.5 41 nM [108]
Pd1.5/PAC-900 DPV Pb2+ 0.5–8.9 55 nM [108]
Pd1.5/PAC-900 DPV Cu2+ 0.5–5.0 66 nM [108]
Pd1.5/PAC-900 DPV Hg2+ 0.24–7.5 54 nM [108]
Au NPs/PANOA ASV Hg2+ 0.8–12.0 nM 0.23 nM [142]
AgNPs/GrNPs/GE SWASV Cd2+ ​ 0.005 μg/L [143]
Pb2+ 0.001 μg/L
Cu2+ 0.0041 μg/L
Ag NPs SWASV Pb2+ 5–160 μg/L 89.1 μg/L [144]
Cd2+ 48 μg/L
Ag–Au NPs/SPCE SWV Cr6+ 0.05–5 ppm 0.1 ppb [145]
AgNPs/RGO SWASV Cd2+ 0.05–1.5 μM 0.141 μM [146]
Pb2+ 0.254 μM
Cu2+ 0.178 μM
Hg2+ 0.285 μM
AgNPs/GrNPs/GCE SWASV Cd2+ 0.5–120 μg/L 5.0 ng/L [143]
Cu2+ 4.1 ng/L
Pb2+ 1.0 ng/L
SnNPs SWV Cd2+ 1–30 μg/L 0.5 μg/L [106]
Zn2+ 0.3 μg/L
SnNPs- RGO/GCS SWASV Cd2+ 10–100 nM 0.63 nM [147]
Pb2+ 0.60 nM
Cu2+ 0.52 nM
Bi-Ni-IPANI/CPE DPASV Ni2+ 0.01–1 μM 0.00482 μM [148]
BiNP/MWCNT-NNaM/PGE Zn2+ 2.36–180.0 μM 0.707 μM
SWASV Cd2+ 0.32–240.0 μM 0.097 μM [110]
Pb2+ 0.03–80.0 μM 0.008 μM
Cu2+ 0.52–40.0 μM 0.157 μM
Bismuth/MBTS SWASV Cu+2 0.25–1.5 ppm 0.34 ppm [149]
(BiO)2CO3-rGO-/Fe3O4-Au SWASV As3+ 2.4 μg/L [150]
Cd2+ 1.2 μg/L 0–50 ppb
Pb2+ 0.8 μg/L
Bi/SPAuE SWASV Pb2+ 1–120 μg/L 0.04 μg/L 0.02 μg/L 0.05 μg/L [151]
Cd2+
Zn2+
Bi-NCNF/GCE SWASV Cd2+ 1–120 μg/L 0.02 μg/L [152]
Pb2+ 0.03 μg/L
Bi NPs/RGO DPASV Cd2+ 20–120 μg/L 2.8 μg/L [153]
Pb2+ 0.55 μg/L
Cu2+ 17 μg/L
Zn2+ 26 μg/L
Pd NPs@PAC/GCE SWASV Cd2+ 25–500 nM 13.33 nM 6.60 nM [154]
Pb2+ 11.92 nM
Cu2+
Pd/PDMS SWCSV Mn2+ 0.455–10.9 µM 334 nM [155]
CNF/Ce DPV Pb2+ 0.9–2.1 μg/L 0.6 μg/L [156]
Cu2+ 0.6–1.8 μg/L 0.3 μg/L
Graphene DPV As3+ 25–500 ppb 3.0 ppb
Cr6+ 0.25–25 ppm 40 ppb [157]
Pb2+ 25–750 ppb 16 ppb
Hg2+ 0.1–1.5 ppm 2.0 ppb
Cd2+ 25–750 ppb 0.95 ppb
G/AuNPs SWASV Hg2+ 0.1 fM – 0.1 μM 50 aM [158]
G/PANI/PS/SPCE SWASV Cd2+ 10–500 μg/L 4.43 μg/L [159]
Pb2+ 3.3 μg/L
MWCNT-CeO2 DPV Hg2+ 1.98 µg/L [160]
Pb2+ 5–5000 µM 1.10 µg/L
Cu2+ 3.53 µg/L
MWCNT@ GO@Fe2O3/PPy SWASV Pb2+ 0.02–0.26 μM 0.1 nM [161]
(continued on next page)

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H. Abd El-Raheem et al. Microchemical Journal 207 (2024) 112086

Table 1 (continued )
Sensing Platform Technique Analyte Sensing range Detection limit Ref.

N-GO-CS-GCE DPV Cd2+ 0.01–0.1 μM 3.51 nM [162]

Graphene oxide SWV Hg2+ 1–20 ppb above 5 ppb [163]
Cr6+
GO/PGA SWASV Cd2+ 2.5 × 10− 7–5.5 × 10− 6
mol/L 1.5 × 10− 8
mol/L [164]
Pb2+
GO-MWCNTs SWASV Cd2+ 30–100 ppm 1.07 × 10 − 12
mol/L [165]
Pb2+

MBTS; mercaptobenzothiazole disulfide.

particular, different voltammetric techniques, such as CV, PV, LSV, HV and oxidation behavior of the material Fig. S1A and S1B, and can be
and stripping voltammetry are widely used for the sensitive and selec- used to predict the capacitive behavior of the electrode. Therefore, it is
tive detection of HMIs (Table 1). These methods are applicable to a wide possible to determine the potential at which the HMIs undergoes
range of sample matrices, including water, soil, and biological fluids, oxidation and reduction reaction [60]. Hence, the concentrations of
and offer fast analysis [53,54]. Additionally, they often require minimal HMIs can be quantitatively determined. The CV technique has been
sample preparation, reducing both time and complexity in the analytical reported to be utilized for detecting HMIs in environmental and bio-
process Scheme1. logical samples with various electrode surfaces. For example, H. Abd El-
Raheem et al. [61] utilized CV to determine the trace amounts of Cu2+ in
4. Description of voltammetric techniques of HMIs detection real biological and environmental samples Fig. S1C. The designed sensor
based on polyurethane doped with platinum nanoparticles displayed a
Voltammetry is an electrochemical technique in which a varying LOD of 16.72 ng mL− 1. A work performed by Wandersonda Silva et al.
potential is applied to an electrochemical cell over time, while the [62] presented a way to detect Hg2+, Pb2+, Cd2+, and Cr6+ using CV. The
resulting current is measured [55,56]. The plot of current against the modified sensor exhibited a LOD of roughly 2 nM, with good selectivity
applied potential generates a voltammogram. This graph offers both and stability. It was successfully used to detect these trace metal ions in
quantitative and qualitative data about the redox reactions’ partici- milk samples with high recovery rates, indicating that it could be helpful
pating species. The information obtained can be useful for identifying in more complex media.
and quantifying the substances involved, as well as understanding their
behavior in different potentials [57]. The first voltammetric method,
called polarography, was developed by Jaroslav Heyrovsky in the early 4.2. Pulse voltammetry (PV) for HMIs detection
1920s, for which he was awarded the Nobel Prize in Chemistry in 1959
[58]. Since then, many forms of voltammetry have been developed. This PV techniques mainly aimed to improve detection limits and permit
technique is crucial for studying redox reactions, adsorption, and elec- convenient quantification down to the 10− 8 M concentration level. The
tron transfer mechanisms at chemically modified electrode surfaces, various pulse methods are based on a sampling current/potential-step
advancing electronic processes in chemical industries, and developing experiment. On the working electrode, a series of potential steps is
corrosion-resistant materials. Voltammetry is frequently used to quan- applied with a duration of about 50 ms. The capacitive current dies
titatively analyze trace metal ions, allowing for the qualitative and much faster than the faradaic current after a potential pulse is applied,
quantitative analysis of HMIs and various organic compounds in solu- hence the current is measured at the end of the pulse. This method of
tion through redox studies [59]. sampling has the benefit of increasing sensitivity and providing superior
characteristics for analytical applications [63].

4.1. Cyclic voltammetry (CV) for HMIs detection 4.2.1. Differential-Pulse voltammetry (DPV) for HMIs detection
In DPV a sequence of constant-amplitude pulses is superimposed on
CV is a fundamental tool for studying materials in an electrochemical the step potential just before the end of the drop. The current is sampled
context. In this technique, the current is recorded while sweeping the twice: once just before the pulse is applied, and again late in the pulse
potential linearly from a negative to a positive value and then back in duration, as shown in Fig. S2A and S2B. The difference between these
the opposite direction. The redox peaks obtained from the graphical two sampled current values helps eliminate the capacitive/background
analysis of a cyclic voltammogram can provide valuable information current during chemical analysis, and focuses on the faradaic current
about the material being studied. These peaks represent the reduction generated by the redox reaction of the analyte. This improves peak

Scheme 1. Classification tree for various voltammetric techniques for HMIs detection.

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H. Abd El-Raheem et al. Microchemical Journal 207 (2024) 112086

resolution and enhances sensitivity. The resulting voltammogram fea- of linearly cycling through the potential range in both directions, LSV
tures current peaks, where the height of each peak is directly propor- consists of a single linear sweep from the lower to the upper potential
tional to the concentration of the respective analytes, and the peak limit. Fig. S6A. LSV has established itself as a rapid and reliable char-
potential can be used to determine the species [64]. Therefore, DPV is acterization method that gives both quantitative and qualitative infor-
one of the most sensitive and selective techniques, offering very low mation on electrochemical systems [70]. For quantitative, Arafat
detection and quantification limits for determining HMIs. Compared to Toghan et al. [74] fabricated a sensor of EDTA-NQS modified glassy
CV, DPV provides higher sensitivity and has been widely studied for carbon electrode to determine Cd2+, Cu2+, Pb2+, Hg2+ and Fe3+. The
HMIs analysis [65]. As an example, Yu, Jiatuo, et al [66] fabricated a LOD was calculated to be between 10.2 and 15.4 nM Fig. S6B. This
(Ni/NiO/ZnO/Chitosan wire) sensor for direct detection of Cu2+ modified sensor was used to detect impurities in a variety of cosmetic
Fig. S2C and S2D. In this case, the interfacial barriers of semiconductor samples with great success.
heterojunctions can serve as a key sensing factor that influences the
electrochemical response. The electrochemical signal was formed by 4.4. Hydrodynamic voltammetry (HV) for HMIs detection
adsorbing Cu2+ causing a change in barrier height in real water samples,
and it displayed outstanding stability and recovery rate with the LOD of HV is a form of voltammetry in which the analyte solution flows
0.81 nM, and a wide detection range of 0–6 µM. towards the working electrode. Convection is used in HV to enhance
mass transfer to the electrode, offering advantages over stagnant solu-
4.2.2. Square wave voltammetry (SWV) for HMIs detection tion approaches. In HV, the current is recorded as a function of the
In addition to DPV, SWV is a highly sensitive electrochemical tech- potential applied to a solid working electrode in a stirred solution [75].
nique. It applies a large amplitude square-wave potential sweep with a Linear scan profiles are employed while the solution moves towards the
stepped potential ramp from an initial to a final potential, where the electrode, using potential profiles similar to those in polarography. Md.
working electrode’s potential alternates between forward and reverse Saiful Islam et al. [76] selected five HMIs Hg2+, Cd2+, Pb2+, Zn2+, and
pulses [67]. In each cycle, the current is measured twice: once at the end Cu2+ to detect in water, based on the inhibition of the alkaline phos-
of the forward pulse and again at the end of the reverse pulse, as illus- phatase (ALP) enzyme from Chlamydomonas reinhardtii. HV with a 50 mL
trated in Fig. S3A and S3B. The resulting voltammogram is peak-shaped micro-droplet and a rotating disk electrode (RDE) was used to assess
and symmetric around the half-wave potential, with the peak current enzyme activity Fig. S7 quickly. The half-maximal enzyme activity
proportional to the concentration. SWV can also be used to quantify (EC50) values were 0.017, 0.021, 0.27, 1.30, and 1.36 μM, respectively,
HMIs, emphasizing highly sensitive, quantitative detection, which is with a LOD of 5.4 × 10− 7 U.
particularly advantageous for trace analysis in complex samples [68]. In
2011, Gemma Aragay et al. [69] reported the use of the SWV method to 4.5. Stripping voltammetry for HMIs detection
detect Cd2+, Pb2+, Cu2+, and Hg2+. The sensing surface, based on carbon
nanoparticle-modified screen-printed electrodes, exhibited linearity in For quantitative analysis, stripping voltammetry is the most sensitive
the concentration range of 5–100 µg L− 1 for Cd2+, Pb2+, and Cu2+, and electrochemical method [77]. It involves two steps: first, the accumu-
1–10 µg L− 1 for Hg2+ Fig. S3C. Preliminary results demonstrated a stable lation of target analytes on the working electrode through controlled
device response during continuous monitoring of 100 ppb Pb2+ in potential electrolysis under convective mass transport; second, the
seawater for up to one month. stripping step, where the accumulated species are removed from the
electrode, generating a current proportional to their concentration,
4.2.3. Normal pulse voltammetry (NPV) for HMIs detection Fig. S8. Three types of stripping voltammetry are commonly used.
NPV involves applying a waveform to non-polarographic electrodes.
In NPV, a sequence of rectangular potential pulses with increasing 4.5.1. Anodic stripping voltammetry (ASV) for HMIs detection
amplitude is applied to successive drops, maintaining a constant pulse ASV is the most common form of stripping analysis and is widely
duration of 10–100 ms near the end of each drop’s lifetime at a fixed DC used to detect trace amounts of HMIs. In ASV, analyte determination is
potential, as illustrated in Fig. S4A and S4B. The pulse amplitude in- based on anodic dissolution. A controlled potential is applied to the
creases linearly with each drop, and the current signal is measured at the working electrode, causing the analyte to preconcentrate on the elec-
end of the potential pulse [70]. Copper ions have been detected Fig. S4C trode surface through electrodeposition. The potential is then scanned
by modifying indium tin oxide (ITO) electrodes with phytate- anodically (toward a more positive potential), stripping the analyte from
functionalized multi-walled carbon nanotubes using differential the electrode back into the solution. Therefore, the primary role of ASV
normal pulse anodic stripping voltammetry. This modified electrode is to detect trace levels of metal ions, such as lead, mercury, and cad-
achieved a LOD of 2.50 × 10− 9 mol L− 1 [71]. mium, with high sensitivity. Its low detection limits and ability to
analyze complex samples make it especially effective for environmental
4.2.4. Staircase voltammetry (SCV) for HMIs detection monitoring. An anodic stripping voltammogram was recorded for Hg2+
SCV involves sweeping the working electrode’s potential linearly detection, using a boron-doped diamond (BDD) thin-film electrode
over time at faster rates than those used in CV. It is typically employed enhanced with copper, achieving a LOD of 0.04 ng.mL− 1 Fig. S9 [78].
for dynamic electrochemical investigations of different substances. In
SCV, a potential staircase is generated to obtain the current response, as 4.5.2. Cathodic stripping voltammetry (CSV) for HMs detection
shown in Fig. S5A and S5B. SCV is intended to operate at a considerably CSV is the reverse of ASV and is used to determine anions. In CSV, the
higher sweep rate and allows for the reversal of the potential scan, analyte is stripped back into the solution by applying a potential sweep
enabling the generation of a cyclic staircase voltammogram [64]. As an toward negative potentials. It is an effective method for detecting metals
example, in 1991, Jørgen Larsen and Bo Svensmark used anodic strip- that form insoluble compounds or complexes, offering an alternative
ping Staircase Voltammetry (ASSV) to determine Pb2+, Zn2+, and Cd2+, approach for HMIs detection when ASV may not be suitable. Addition-
Fig. S5C [72]. ally, CSV exhibits high selectivity and sensitivity. In 2001, Clinio
Locatelli and Giancarlo Torsi [79] reported using the CSV approach to
4.3. Linear sweep voltammetry (LSV) for HMIs detection detect As3+ and Se4+ in environmental samples, with detection limits for
each element around of 10− 9 mol L− 1 Fig. S10.
The simplest form of voltammetry is known as LSV, where the po-
tential is linearly swept between final and beginning values as a function 4.5.3. Adsorptive stripping voltammetry (AdSV) for HMs detection
of time while the current is recorded [73]. LSV resembles CV, but instead In AdSV, HMIs are initially adsorbed onto the electrode surface in a

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preconcentration step. This process enhances the concentration of the 5.1.1. Platinum nanoparticles (PtNPs)
target ion on the electrode, thereby amplifying the signal during the Due to their unique electrical and electrocatalytic properties, PtNPs
voltammetric measurement. By pre-concentrating the analyte AdSV can have garnered significant interest in electrochemical sensors for various
detect trace levels of HMIs, often reaching down to nanomolar con- environmental applications. The characteristics of PtNPs are highly
centrations. This capability renders it particularly valuable for envi- influenced by their chemical reactivity, electronic properties, and
ronmental and biomedical applications where low detection limits are of interatomic bond distances, which are structure-dependent [88,89]. As a
paramount importance [80]. For example, trace amounts of total chro- result, the development of electrode surfaces with PtNPs provides
mium [Cr3+ and Cr6+] Fig. S11 have been determined in natural water excellent stability, chemical inertness, low background current, and
based on the preconcentration of the Cr(III)-DTPA complex by adsorp- high catalytic and sensing performance [90,91]. For instance, Dai et al.
tion and then reduced producing a response with a peak potential of used spherical PtNPs, with diameters ranging from 105 to 180 nm,
− 1.22 V [81]. electrodeposited on a GCE to detect As3+. CV was applied as the
detection technique, yielding a LOD of 35 µg L− 1 [92]. Hrapovic et al.
5. Nanomaterials (NMs) as electrode for HMIs detection electrodeposited spherical Pt NPs on a boron-doped diamond electrode
for the detection of Arsenite (III) using LSV, the boron-doped electrode
The effectiveness of voltammetric detection of HMIs is highly influ- was proven to have a superior performance with a LOD of 0.5 µg/L [93].
enced by the characteristics of the electrode. Thus, the surface modifi- Abd El-Raheem et al. used polyurethane doped with platinum nano-
cation of the working electrode can significantly improve the specific particles (PU/Pt NPs) of the average size of 2–5 nm as a sensing platform
recognition and concentration of metal ions. These modifications can be for the direct detection of Cu2+ using CV Fig. S12 [61].
achieved through various methods, one of these ways applying other
materials to the electrode’s surface. Nanomaterials, ranging in size from 5.1.2. Gold nanoparticles (AuNPs)
1 to 100 nm-including metal nanoparticles (NPs), metal oxides, semi- AuNPs, or gold colloids, are the most stable metal nanoparticles,
conductor quantum dots (QDs), carbon-based materials, and hybrid characterized by sizes between 1 and 100 nm and possessing unique
nanomaterials such as NP-modified carbon nanomaterials or organic properties that are not present in bulk materials [94,95]. The intrinsic
polymer NPs—can induce these changes [82]. These nanomaterials characteristics of Au NPs offer various advantages in the manufacturing
possess unique physical and chemical properties distinct from their bulk of smart sensors from a sensing standpoint, due to their control of shape
counterparts. Furthermore, they can be designed to yield sensitive re- and size by varying experimental conditions to give a distinct electrical
sults with greater selectivity by being synthesized with carefully characteristic [96,97]. Also, AuNPs serve as an ideal framework for
controlled sizes, morphologies, charges, and physicochemical properties immobilizing large numbers of certain functional groups, resulting in
[83]. So, electrochemical reactions can be accelerated, surface kinetics quick responses and great sensitivity for the targeted analyte due to their
enhanced, analyte adsorption improved, and method selectivity huge surface area to volume ratio. AuNPs are modified on the surface of
increased through functionalization of the active regions [83]. SPEs. For instance, Zhang, Lei, et al [98] used AuNPs amalgam modified
SPE for the monitoring of Cd2+ in real water samples. The response
current is linear to concentration within the range between 8.4 and 500
5.1. Metal nanoparticles ppm and a LOD of 2.6 ppb by ASV. Other researchers [99] have detected
chromium (VI) based on a SPCE with AuNPs modification At the opti-
Metallic nanoparticles have been widely utilized as electrode mate- mized conditions, the calibration curve for chromium (VI) shows a
rials for detecting various target analytes in environmental monitoring sensitivity of 1.1 nA(μg/L)− 1 with a LOD of 0.4 μg/L by LSV. Poly(ester-
[84]. These nanoparticles play critical roles in electrode design, offering urethane) urea doped with gold nanoparticles (PUU/Au NPs) was
easy surface functionalization, facilitating sensor construction, cata- employed to modify a carbon paste electrode for the highly sensitive
lyzing electrochemical reactions, and enhancing electron transfer pro- detection of Hg2+ in fish tissue Fig. S13 [100].
cesses [85]. Among various metallic nanoparticles, precious metals such
as Pt, Au, Ag, Sn, Pd, and Bi [86] often combined with other functional 5.1.3. Silver nanoparticles (AgNPs)
materials [87], have been extensively studied and applied as promising Due to their high conductivity, enhanced electrochemical signal, and
candidates for quantifying a wide range of HMIs using various voltam- remarkable biocompatibility, AgNPs have emerged as one of the most
metric techniques. promising nanomaterials for electrochemical and biosensing

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applications. The development of AgNP-based sensors has significantly good electrical conductivity, mechanical, easy modifiability, high
impacted the analysis of HMIs due to their high sensitivity and speci- reproducibility, and chemical properties [115]. Carbon nanomaterials
ficity [101,102]. For instance, to assess Hg2+ concentration, Suherman include carbon nanoparticles (CNPs), carbon nanofibers (CNFs), carbon
et al. developed a GCE modified with AgNPs (GCE/AgNPs) [103]. The nanohorns (CNHs), graphene (GR), and graphene oxide (GO). In this
LSV results showed a linear range of 100.0 pM–10.0 nM and a LOD of 28 section, we summarized the latest developments and applications of
pM for Hg2+. Another study utilized AgNPs embedded in a thin-film carbon nanomaterials with other functional materials as working elec-
chitosan matrix (AgNPs/CT) for the detection of As3+ using differen- trodes for HMIs determination.
tial pulse anodic stripping voltammetry (DPASV) [104]. The designed
electrode exhibited a LOD of 1.20 ppb, significantly lower than the 5.2.1. Carbon nanoparticles (CNPs)
arsenic limit of 10 ppb in drinking water set by the WHO. CNPs were initially described as “fluorescent carbon” by Scrivens in
2004 [116]. Over time, they have been referred to as carbon dots (C-
5.1.4. Tin Nanoparticles (SnNPs) dots) for particles smaller than 10 nm and CNPs for those that are
SnNPs possess desirable physical, chemical, and electronic properties approximately 10 nm or larger. These particles typically exhibit a quasi-
for various applications, including lithium battery anode materials, spherical shape and consist of cores that range from amorphous to
inkjet printing, lead-free solders, and electrochemical sensors [105]. nanocrystalline [117]. CNPs/C-dots exhibit exceptional electronic
Due to their good electrical conductivity, mechanical stability, and characteristics as electron donors and acceptors, enabling a wide range
thermal stability, Sn nanomaterials have been utilized to modify work- of applications. The use of CNPs for detecting HMIs was first achieved by
ing electrodes for detecting HMIs. For example, Trachioti et al. modified Aaron Simpson et al. [118] in 2018. GCEs were modified by drop casting
graphite screen-printed electrodes (GSPEs) with SnNPs for the deter- CNPs and used for the detection of Cu2+ and Pb2+ using SWASV Fig. S16.
mination of Cd2+ and Zn2+ using ASV [106]. Sn NPs with sizes ranging The detection limits for Cu2+ and Pb2+ were 0.50 ppm and 0.30 ppm.
from 20 to 30 nm were produced using a sparking method with a Sn tip
as the sparking source and were deposited on the surface of the SPCE. 5.2.2. Carbon nanofibers (CNFs)
The amount of SnNPs deposited was controlled by the number of CNFs are a type of carbon fiber that has been scaled down to the
sparking cycles, as shown in Fig. S14. The modified sensor was suc- nanometer level. It is a quasi-one-dimensional carbon material that lies
cessfully applied to determine Cd2+ and Zn2+ in tap and bottled water between carbon nanotubes and carbon fibers. Based on structural
samples. properties, it may be divided into two types: hollow carbon nanofiber
and solid carbon nanofiber. It has a diameter of 10 to 500 nm and a
5.1.5. Palladium nanoparticles (Pd NPs) length of 0.5 to 200 μm. CNFs are synthesized by chemical vapor
Pd NPs are an appealing class of versatile nanomaterials used in deposition, electrospinning, templating, drawing, and phase separation.
various applications, including catalytic reduction, hydrogen generation CNFs have a wide range of applications, including nanocomposites,
and storage, methane combustion, lithium-ion batteries, super- photocatalysis, energy devices, catalyst supports, filtration, medication
capacitors, organic synthesis, and chemical/biological sensors [107]. delivery, tissue engineering, and sensors. Robinson et al [119]. First
PdNPs are generally spherical and have a size range of 0.95–35 nm. used for CNFs in the form of vertically aligned carbon nanofiber
Owing to this, dispersed Pd NPs on porous activated carbons were used (VACNF)-based nanoelectrode arrays Fig. S17, to detect Pb2+ by ASV
for the modification of glassy carbon electrode to detect various Cd2+, with LOD of 1.73 nM.
Pb2+, Cu2+, and Hg2+ [108].
5.2.3. Carbon nanohorns (CNHs)
5.1.6. Bismuth nanoparticles (Bi NPs) CNHs are conical-shaped carbon nanostructures commonly referred
The use of bismuth as an electrode for metal ion detection has been to as carbon nanocones. They belong to a class of one-dimensional
demonstrated in innovative research by Wang et al [109] revealing the carbon nanostructures that possess unique features compared to other
tremendous potential of bismuth as a “green metal” in electroanalysis. carbon nanostructures [120]. Harris et al. were the first to investigate
Moreover, the Bi-modified electrode has a high sensitivity and a wide carbon nanohorns, which are derived from the waste product of shoots
range of working electric potential that is unaffected by dissolved oxy- formed during the production of fullerene via the arc discharge process
gen [110]. Furthermore, Bi-NPs could be designed in various shapes and [121]. Upon heating to 2500–3500 K using a positive-hearth electron
sizes for sensing HMIs. For instance, the square wave anodic stripping gun, carbon nanohorns are converted into two forms: single-walled
voltammetry technique was used to detect Zn2+, Cd2+, and Pb2+ [111]. carbon nanohorns (SWCNHs) and multi-walled carbon nanohorns
BiNPs were synthesized and adhered to the surface of SPCE using a (MWCNHs) [122]. CNHs are considered a viable replacement for carbon
Nafion binder to maintain the coating on the electrode surface. For all nanotubes due to their high yield, high purity, large specific surface
target ions, a linear range of 1.0–60.0 µg.L− 1 was observed, with LOD of area, chemical stability, low toxicity, exceptional catalytic properties,
0.05 µg.L− 1 for Zn2+, 0.09 µg.L− 1 for Cd2+, and 0.16 µg.L− 1 for Pb2+. To superior porosity, and good conductivity. These characteristics have
enhance performance, BiNPs have been combined with other nano- expanded their applications to include electrochemical sensing or bio-
materials for the determination of HMIs. For example, porous bismuth- sensing and biofuel cells as electrode materials [121,123]. To create a
carbon aerogels (Bi-CA) and xerogels (Bi-CX) were dispersed in chitosan disposable sensor based on SWCNHs, the SWASV technique was
solution and deposited on the surface of GCE as electrode materials for employed to detect Cd2+ and Pb2+ ions, achieving LOD of 0.2 and 0.4 μg
detecting Pb2+ and Cd2+ Fig. S15 [112]. The obtained results for L− 1, respectively, by Yao et al. [124].
modified electrodes, GCE/Chi-(Bi-CX) and GCE/Chi-(Bi-CA) were 0.16
ppb and 0.02 ppb for Pb2+ and Cd2+ respectively with linear range 5.2.4. Carbon nanotubes (CNTs)
0.2–1 ppb by using SWASV. CNTs are classified as one-dimensional (1D) carbon nanomaterials
made up of sp2 hybridized carbon atoms that form rolled graphene
5.2. Carbon-based materials sheets. They are structured in a hollow tubular form with diameters
ranging from 1 to 100 nm. CNTs are categorized into SWCNTs, which
Carbon-based nanomaterials have gotten a lot of interest since the consist of a single rolled layer of graphene with lengths on the order of
discovery of C60 in 1985 [113] and carbon nanotubes (CNTS) in 1991 1–100 μm, and MWCNTs, which are made up of multiple graphene
[114] as one of the most efficient nanostructured carbonaceous mate- sheets rolled to create tubes with a shared central axis and a separation
rials that have been extensively employed for the fabrication of elec- distance of 0.34 nm. CNTs have been recognized as a promising material
trochemical sensors for the detection of various species. Due to their for signal transduction in biosensors due to their chemical stability, low

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conductivity but also facilitates effective analyte molecule attachment

and rapid electron transfer, leading to increased sensitivity in graphene-
modified electrodes. The direct incorporation of graphene into printing
ink is the preferred method for fabricating SPEs. For example, graphene
paste was deposited on a screen-printed carbon working electrode, and
the DPV method was applied for the rapid detection of trace Cd2+ in rice
samples [132].

5.2.6. Graphene oxide

GO is a material that is similar to graphene but it contains oxygen
based-functional groups in its structure [133,134]. The most common
Fig. 1. Schematic illustration of biosensor for different target analytes. way to get graphene oxide is to oxidize graphite, which is a multilayer
form of graphene. Oxidation of the graphene (with –O and –OH) in-
residual current, rapidly renewable surface, faster electron transfer ki- creases the bond length between C–C and results in a lowering of the
netics, increased currents, and broad potential window [125,126]. The elasticity and tensile strength of the graphene oxide [135]. In compar-
engineered MWCNTs exhibited attractive electroanalytical performance ison to graphene, graphene oxide possesses distinct mechanical, elec-
in the detection of Cd2+ and Pb2+ under optimal conditions using trical, and thermal properties. GO is commonly employed, in a wide
SWASV. The LOD for Cd2+ and Pb2+ were calculated to be 0.4 μg L− 1 and range of sensor applications [136]. Here, GO modified screen-printed
0.3 μg L− 1, respectively [127]. carbon electrode (GO/SPCE) was used to determine of Cd2+, Pb2+,
Cu2+ and Hg2+ based on a sequential injection (SI), coupled with
5.2.5. Graphene SWASV, under the optimal conditions, the sensor has exhibited a linear
Graphene consists of a single layer of carbon atoms linked by over- range from 0.1 to 1.5 M and LOD were 0.054, 0.026, 0.060, and 0.066
lapping sp2 hybrid bonds. Its exceptional properties originate from the µM, respectively [137].
2p orbitals, which enable the p bands to traverse the carbon sheets that
constitute the graphene structure [128,129]. Since its discovery in 2004, 6. Biosensor
graphene has become a major focus of research. It is one of the strongest
known materials, with a tensile strength of 130.5 GPa and a Young’s A biosensor generally comprises a bioreceptor, a physicochemical
modulus of 1 TPa [129,130]. In addition to its excellent electrical con- detector, and a transducer. The bioreceptor, which may be a biomole-
ductivity (64 mS cm− 1) and large surface area (theoretically 2630 m2 cule like an aptamer, antibody, nucleic acid, enzyme, or cell, is
g− 1) [131]. Graphene demonstrates outstanding electrochemical prop- responsible for identifying the target analyte, Fig. 1 [166]. It is designed
erties, including high electrochemical activity, a broad potential win- to have high specificity for the target analyte, meaning it binds exclu-
dow, low charge-transfer resistance, and rapid electron transfer rates sively to that substance, avoiding interactions with others [166]. This
[131]. Its extensive surface area not only enhances electrical specific interaction prevents interference from non-target substances,

Table 2
Summarizes examples of Electrochemical aptasensors for the detection of HMIs.
Sensing Platform Aptamer Technique Analyte Sensing range LOD Ref.

AuNPs/Ti3C2- 5′-GGG TGG GTG GGT GGG T-C6-SH-3′ SWV Pb2+ 5 × 10− 7–3 × 3 × 10− 7 [205]
MXene) 10− 4 M M
Ti- modified Co3O4 5ʹ-GGACTGTTGTGGTATTAT TTTTGGTTGTGCAGTCC-3ʹ CV Cd2+ 1.8 × 4.36 × [206]
10− 3–0.13 nM 10− 3 nM
Pt nanotubes 5′–SH–(CH2)6-ACCGTGTTTGCCTTTGACCTC-3′ DPV Hg2+ 0.1–100 nM 0.03 nM [207]
Thionine labelled 5′-GCTGTCGGATGAGGTCTTTGGCTTTCACGGT-3′
Fe3O4/rGO NPs
Fe3O4@Au NPs 5′–SH–AAAATCACCCATGAGGCATCTTTAGCG-3′; SWV Hg2+ 10–100 nM 1.7 nM [208]
5′- Fc-TCATCCGTGAT-3′;
5′- MB-CGCTTTAGATG-3′
Au NPs polypyrrole 5′-GGGTGGGTGGGTGGGT-3′; 5′-CCACCCACCCe(CH2)6-SH-3′ DPV Pb2+ 2.4–120 nM 2.9 nM [185]
CeO2 5′-MB-AAAAA-3′ DPV As5+ 50–2000 nM 20.5 nM [209]
Fe3O4@Au NPs 5′–SH–AAAATCACCCATGAGGCATCTTTAGCG-3′; SWV Ag+ 0–400 nM 3.4 nM [208]
5′- Fc-TCATCCGTGAT-3′;
5′- MB-CGCTTTAGATG-3′
Au NPs polypyrrole 5-GGGTGGGTGGGTGGGT-3 DPV Pb2+ 0.5–10 nM 0.36 nM [210]
Ag@Au core shell 5′-CCC CCC CCC CCC TTC TTT CTT CCC CTT GTT TGT T-3′ SWV Hg2+ 0.01–0.16 nM 6 × 10− 3 [211]
nM
Au NPs/CS 5′-HSe(CH2)6-ACCGACCGTGCTGGACTCTGGACTGTTGTGGTATTA DPV Cd2+ 0.001–100 nM 0.049 × [212]
TTTTTGGTTGTGCAGTATGAGCGAGCGTTGCG-3′ 10− 3 nM
2+
rGO/Au nanorods 5′-SHTTTTTT T-3′; 5′-biotin-TTT TTT T-3′ DPV Hg 1–200 nM 0.24 nM [213]
Au NPs 5′-HS-GCGCGCGCCCTTTTTCCCCCCCCCGCGCGCGC biotin-3′; 5′-FAM- DPV Hg2+ 0.35 × 0.21 × [214]
GCGCGCGCCCTTTTTCCCCCCCCCGCGCGCGC-Dabcyl-3′; 5′-TTTTGGGCGAACACACAC- 10− 3–3.5 nM 10− 3 nM
3′;
Au NPs 5′-SH-(CH2)6-TTCTTTCTTCGCGTTGTTTGTT-MB-3′ SWV Hg2+ 1 × 10− 6–1 nM 0.62 × [215]
10− 6 nM
2+
Au@Ag core shell 5′-SHe(CH2)6-AAA ATT TTG CTT TGG TTT-3′; 5′-SHe(CH2)6-AAA AAT TTC CTT TGC SWV Hg 9.97 × 2.99 × [216]
TTT-3′; 5′-eSHe(CH2)6-GGG TAG GGC GGG TTG GGT-3′ 10− 3–99.7 nM 10− 3 nM
2+
Au NPs-thionine 5′-GGGTGGGTGGGTGGGT-3′; DPV Pb 1–40 nM 0.374 nM [217]
5′-Thiol-GAGGACCCACCCACCCACCCTCCTCAAThiol-3
Fe3O4@Au NPs 5′-SHeAAAATCACCCATGAGGCATCTTTAGCG-3′; 5′- Fc-TCATCCGTGAT-3′; SWV Ag+ 0–400 nM 3.4 nM [208]
5′- MB-CGCTTTAGATG-3′
Au/MoS2-MWCNT 5′-SH-C6-CGGCTTTTGTTTT-3′ DPV Hg2+ 0.1–1000 nM 0.05 nM [218]

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Fig. 2. Design of Hg2+ aptasensor by dsDNA gold electrode in the presence of zM to pM concentrations of Hg2+, Copyright © 2018. Licensee MDPI [175].

ensuring an accurate biosensor signal. The transducer then converts the molecules, as the biorecognition element. These aptamers are engi-
bioreceptor’s recognition event into a measurable signal. Biosensors are neered to bind selectively to target molecules such as proteins, small
widely used in point-of-care diagnostics, detecting genetic conditions molecules, or cell surface receptors. Upon binding, they trigger a
such as cancer and diabetes, analyzing biological samples, monitoring response detectable by a physicochemical sensor, classifying aptasensors
environmental conditions, drug discovery, soil quality assessment, as a type of biosensor [169]. Aptasensors offer several advantages over
water management, and food quality control [167,168]. other biosensors. They are easy to manufacture and customize and can
be designed to detect a wide range of target molecules. Additionally,
they exhibit high specificity and sensitivity, capable of detecting very
6.1. Aptasensors
low concentrations of the target [170]. Furthermore, aptasensors are
reusable, making them a cost-effective option for continuous
Aptasensors use aptamers, short single-stranded DNA or RNA

Fig. 3. (A) Diagram of the design of the aptamer-TdT based amplification system for Hg2+ detection. (B) Oxidized form and reduced form of methylene blue (MB),
Copyright © 2018 Licensee MDPI [177]. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

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H. Abd El-Raheem et al. Microchemical Journal 207 (2024) 112086

monitoring. aptamer detected Hg2+ by folding into a hairpin structure, bringing the
electrochemical signal close to the sensor surface, thereby triggering an
6.1.1. Aptasensors for HMIs detection electrochemical reaction. Due to this mechanism, the logarithm of Hg2+
Aptasensors offer high specificity, sensitivity, and ease of prepara- concentration showed a strong linear relationship with the DPV peak
tion for small molecule detection, providing a promising platform for current in the range of 0.01–500 nM, with a LOD of 5 nM for the
HMIs detection, (Table 2). However, detecting HMIs with aptamers is fabricated sensor [176]. In another study, Si et al. developed an elec-
more challenging than with other targets due to their simple structure trochemical sensor for Hg2+ detection, utilizing the thymine-rich
and unique interaction sites [171]. The interaction between HMIs and aptamer’s selectivity for Hg2+ and the high catalytic activity of termi-
aptamers does not result in a significant mass increase or a steric nal deoxynucleotidyl transferase (TdT), Fig. 3-. The TdT enzyme
entrapment effect, which limits the sensitivity and application of many increased the sensor’s sensitivity by extending the bases at the 3′-OH end
aptasensors [172]. Despite these challenges, HMIs aptasensors exhibit of the aptamer, while the Hg2+ aptamer facilitated selective thymine
advantages such as high sensitivity and fast response times, making pair interactions, improving both specificity and sensitivity. Using this
them competitive with conventional detectors. This section discusses method, the sensor achieved a LOD of 0.1 pM [177].
effective methods for detecting HMIs using aptasensors [173]. In another aptamer-based study, Tang et al. developed an aptasensor
with a single-screen printed multichannel carbon electrode using open-
6.1.2. Aptasensors for mercury detection circuit potential (OCP) technology for the simultaneous detection of
Even at low concentrations, mercury is one of the most toxic, posing three HMIs Hg2+, Cd2+, and As3+, with LOD of 2, 0.62, and 0.17 pmol
significant risks to ecosystems and human health. It accumulates in L− 1, respectively [178]. In a separate study, Diaz-Amaya et al. investi-
lakes, wetlands, and soils due to industrial and agricultural activities or gated an aptamer-based sensor using an inkjet-printed gold electrode as
is converted by organisms into the more harmful methylmercury form. a reliable, stable, and scalable method for detecting Hg2+ in water and
Mercury ions (Hg2+) bind to enzymes that catalyze critical metabolic organic solvents. The results demonstrated good stability and repeat-
processes in humans, leading to serious health issues such as kidney ability of the aptasensor under challenging conditions. The platform
failure, brain damage, cardiovascular complications, or even death. One achieved a LOD of 0.01 ppm in water and exhibited a twofold increase in
approach to mercury detection involves an ultra-sensitive, highly se- sensitivity in organic solvents, with a LOD of 0.005 ppm [179]. Zhao
lective, label-free electrochemical aptasensor for the quantitative et al. reported an electrochemical aptasensor for HMIs detection using
detection of Hg2+ at zeptomolar concentrations. In this design, Amiri thiol-reduced graphene (Au@HS-rGO) and thymine-Hg2+ (T-Hg2+-T)
et al. [174] Substituted thiol groups in single-stranded DNA (ssDNA), complexes. First, an Au@HS-rGO substrate was generated on the surface
which self-assembled on a gold electrode via S-Au interactions. The of a GCE, enabling the attachment of single-stranded DNA. Thionin was
hybridization of ssDNA with complementary DNA (cDNA) and the then immobilized on the electrode surface, and Hg2+ was detected using
dehybridization induced by Hg2+ were monitored using DPV with a DPV. The aptasensor exhibited a LOD of 0.38 nmol L− 1 [180].
redox probe ([Fe(CN)6]3− /4− ) Fig. 2. A significant phenomenon for In a study by Wang et al. gold-modified thiol-graphene (Au@HS-
detecting Hg2+ in environmental samples is the formation of a thymine- rGO) was developed and used as a sensing platform to construct an
Hg2+-thymine complex [175]. electrochemical aptasensor Fig. 4. Gold-palladium modified zirconium
Liu et al. developed an electrochemical Hg2+ aptasensor based on the organometallic framework nanozymes were employed as signal ampli-
thymine-Hg2+-thymine (T-Hg2+-T) structure and successfully applied it fiers for the detection of Hg2+. Under optimal conditions, the electro-
to detect Hg2+ in tap water samples. To enhance electron transport and chemical aptasensor demonstrated a wide linear range from 1.0 nmol
analytical response, the GCE was modified with AuNPs and chitosan L− 1 to 1.0 mM, with a LOD of 0.16 nM [181]. Recently, Salandari-Jolge
functionalized with the aptamer (aptamer/AuNPs/CS/GCE). The et al. synthesized an ultrasensitive electrochemical aptasensor based on

Fig. 4. Schematic diagram of the Hg2+ aptasensor, Copyright © 2021 Elsevier B.V. [182].

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Fig. 5. Schematic illustration for electrochemical biosensing system constructed by aptasensor/Au@Py for Pb+2 detection [185].

Fig. 6. Assembly of the electrochemical aptasensor, Copyright © 2021 Elsevier B.V. [187].

zeolitic imidazolate framework-8 (ZIF-8) derived Ag/Au core–shell indicator, interacting with the DNA double strand (dsDNA) formed by
nanoparticles for the detection of Hg2+ in water samples. Under optimal the Pb2+ aptamer and its complementary strand. The peak current of the
conditions, the aptasensor exhibited wide linear ranges of 10− 16–10− 12 interaction between TB and dsDNA decreased in the presence of Pb2+
M and 5 × 10− 15–10− 12 M using DPV and EIS, respectively. Further- compared to its absence. Under optimal conditions, the sensor detected
more, the developed aptasensor achieved an ultralow LOD of 10− 17 M Pb2+ in the range of 0.5–25 ppb, with a LOD of 0.6 ppb [185].
Hg2+ with DPV and 10− 16 M Hg2+ with EIS [182]. Wang et al. presented an electrochemical aptasensor for the deter-
mination of Pb2+ based on the modification of gold with a nano-
6.1.3. Aptasensors for lead detection composite of graphene. Porous reduced graphene oxide (rGO) was
Electrochemical aptasensors for Pb2+ detection primarily utilize G- attached to the gold surface, and Au@p-rGO was used as a platform for
quadruplex DNA capture. This DNA sequence specifically targets Pb2+ the immobilization of the aptamer strand (Apt1). Two types of aptamers
using principles similar to those in other detection methods. The key to were employed to fabricate the sensor: a sulfhydryl-labeled substrate
developing a highly sensitive sensor lies in the binding of nanomaterials strand (Apt1) and a sulfhydryl-labeled catalytic strand (Apt2). Apt2,
to the aptamer [183]. Yu et al. developed a highly sensitive electro- functionalized with modified AuNPs@GO, acted as a signal probe to
chemical sensor for Pb2+ detection based on an aptamer G-quadruplex monitor its immobilization on the electrode surface. This aptasensor
and an electrochemically reduced graphene oxide (ErGO) electrode. demonstrated a LOD of 1.67 pmol L− 1 [186]. Recently, a composite of
Methylene blue (MB) G-rich aptamers were immobilized on an ErGO- chitosan, graphene, and titanium dioxide (CS/rGO/TiO2) was prepared
modified GCE via π-interaction. Upon the introduction of Pb2+, the for the detection of Pb2+ Fig. 6. The complementary aptamer strand was
aptamer recognized the allosteric G-quadruplexes generated by Pb2+ mounted on the surface of the modified electrode to hybridize with the
and detached from the ErGO surface, leading to a significant shift in the Pb2+ aptamer, forming a double-stranded DNA structure. In the pres-
redox current at MB. The sensor demonstrated a LOD of 0.51 fM for Pb2+ ence of Pb2+, the DNA duplex unfolds, forming a stable G-quadruplex
[184]. Ding et al. developed an electrochemical sensor for Pb2+ detec- due to the induced aptamer conformation. Under optimal conditions,
tion using a Pb2+-specific aptamer combined with AuNPs composites the modified electrode could detect Pb2+ in the range of 1 ng L− 1–1000
and polypyrrole (Au@Py) Fig. 5. When Au@Py was applied to the sur- ng L− 1, with a LOD of 0.33 ng L− 1 [187].
face of a SPE, the AuNPs in the composite enhanced signal transduction
and amplified the current. Toluidine blue (TB) served as a redox

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Fig. 7. Schematic illustration of GCE chemical surface modification with CNTs-AuNPs/CS nanocomposite for aptamer immobilization and application in cadmium
detection, Copyright © 2021 MDPI [191].

Fig. 8. Metal ion detection using DNAzyme-based biosensing platforms. (a) A hybridization chain reaction-based horseradish peroxidase concatemer sensing system
for Cu2+ detection. (b) A nanoparticle-based lateral flow test strips for Pb2+ detection. (c) AuNPs for plasmonic detection of Pb2+ ions [195].

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6.1.4. Aptasensors for cadmium detection of 0.65 fM [190]. In 2021, Rabai et al. successfully developed a label-
Monitoring Cd2+ concentrations in environmental water are critical free aptasensor for Cd2+ detection in water samples, as shown in
due to its toxicity and persistent accumulation, which poses a significant Fig. 7. The aptamer was crosslinked to a GCE via a nanocomposite of
threat to living organisms. Industrial effluents are the primary source of CNTs, AuNPs, and chitosan. AuNPs were deposited onto the CNTs/CS/
Cd2+ pollution in water bodies. Cadmium tends to accumulate in organs GCE using chronoamperometry, and the amino-modified Cd2+ aptamer
such as the kidneys, liver, and lungs, as the body lacks a detoxification was immobilized via glutaraldehyde crosslinking. EIS was used for
pathway to eliminate Cd2+ ions. This accumulation can lead to cadmium cadmium determination, with the aptasensor demonstrating a highly
poisoning, which is associated with kidney dysfunction, cancer, and sensitive LOD of 0.02 pM. The response was linear across a range of
hypertension. To protect public health, routine and effective monitoring 10− 13–10− 4 M [191].
of Cd2+ levels in drinking water is essential [188]. In recent years,
several reports have highlighted the development of electrochemical 6.1.5. Aptasensors for other HMIs detection
aptasensors for Cd2+ detection. Fakude et al. developed a label-free Numerous studies have been conducted on the electrochemical
electrochemical aptasensor for Cd2+ by immobilizing a Cd2+-binding aptasensing of As3+. For example, Mushiana et al. (2019) reported an
thiolated single-stranded DNA (SH-ssDNA) aptamer on a SPCE modified electrochemical aptasensor based on the Ars-3 aptamer and a carbon
with carbon black (CB) nanoparticles and AuNPs. The nanoplatform was and gold nanoplatform (CNPs/AuNPs). The thiol-modified Ars-3
prepared by drop-casting CB and electrodepositing AuNPs using a cyclic aptamer was immobilized on a GCE modified with CNPs/AuNPs via an
potential range from − 400 mV to 1100 mV at a scan rate of 50 mV/s. Au-S bond. The CNPs effectively amplified the electrochemical signal of
The 36-base thiolated ssDNA aptamer immobilized on the SPCE-CB- As3+ in combination with As3+ on the surface of the AuNPs, achieving a
AuNPs underwent a conformational change upon interaction with LOD of 0.092 ppb. Similarly, Yadav and colleagues developed an elec-
Cd2+, resulting in a shift in the electrochemical current response. The trochemical aptasensor using Ag-Au alloy nanomaterials (Ag-Au alloy
aptasensor detected Cd2+ in a linear range of 1–50 ppb, with a LOD of NPs) for As3+ detection. The sensor utilized an Ars-3 aptamer deeply
0.14 ppb [188]. In 2020, the same group developed an aptasensor by entrapped within the Ag-Au alloy nanomaterials, which were used to
immobilizing a biotinylated aptamer specific for Cd2+ onto an activated modify the GCE. The entrapped As3+ initiated an electrochemical re-
carbon nanofiber (CNF) and a streptavidin-modified SPE. CV, SWV, and action, leading to a significant increase in the current observed in the
EIS were used to characterize each step of the aptamer preparation. The voltammetry curves. This sensor achieved a LOD of 3 pg L− 1 [192,193].
aptasensor demonstrated a LOD of 0.11 ppb and a linear range of 2–100
ppb for Cd2+ [189]. Chang-Seuk Lee et al. fabricated an aptasensor
6.2. Biosensors based on DNA-zymes
based on a structure-switching aptamer duplex immobilized on an
electrochemically reduced graphene oxide (ErGO) electrode (cDNA-
Various biomolecules, such as DNAzymes, have been designed to
Apt/MB/ErGO/GCE) for the ultra-trace detection of Cd2+ ions. This
target metal ions. Biosensors based on DNAzymes can specifically detect
method employed a methylene blue (MB)-labeled aptamer probe (Apt)
certain metal ions due to their catalytic reactions and DNA cleavage
and its partially complementary DNA (cDNA) to form an aptamer duplex
capabilities. DNAzymes are single-stranded (ss) DNA sequences that fold
(cDNA-Apt), which was immobilized on the ErGO electrode. The prox-
into complex tertiary structures and catalyze reactions, including the
imity of MB to the electrode inhibited efficient electron transfer, leading
cleavage of the phosphodiester backbone at ribonucleotide or deoxyri-
to a reduced oxidation peak current. In the presence of Cd2+, the cDNA-
bonucleotide sites. Metal ions play a critical role in these catalytic pro-
Apt duplex unwound, releasing the cDNA and enhancing electron
cesses and are essential for the activity of most known DNAzymes Fig. 8
transfer efficiency, which increased the electrochemical signal. This
[194].
sensor could detect Cd2+ concentrations from 1 fM to 1 nM, with a LOD
Many studies have focused on the sensitive analysis of various HMIs

Fig. 9. (a) Schematic illustration of OTAB release after the binding of Pb2+ to the DNAzyme; with planar configuration and corresponding optical image of the LC
droplets without the OTAB arrangement; homeotropic configuration and corresponding optical image of the LC droplets with the OTAB arrangement at the aqueous/
LC interface [200].

13
H. Abd El-Raheem et al. Microchemical Journal 207 (2024) 112086

Fig. 10. Schematic diagram of the SERS detection system for Pb2+ [203].

using DNAzymes. For example, Wang et al. functionalized multilayer for Pb2+ detection. AuNPs were deposited on the electrode surface to
reduced graphene oxide (rGO) with amino groups via nitrogen plasma immobilize a thiol-modified DNA probe, which hybridized with catalytic
treatment. The amino-modified rGO was then used to develop an elec- DNAzyme tags. In the presence of Pb2+, the DNAzyme cleaved the
trochemical biosensor, where a DNAzyme, substrate DNA, and binding substrate strand, altering the electrical properties of the film. The
DNA for Pb2+ and Hg2+ were immobilized on the rGO-modified gold change in charge transfer resistance (RCT) values was linearly related to
electrode. The high concentration of amino groups and the rough sur- Pb2+ concentration, with a LOD of 0.2 nM [197]. In another study,
face of rGO facilitated DNA immobilization. HMIs were detected Skotadis et al. used PtNPs, with a diameter of 5 nm, deposited on
through specific interactions between the DNA and metal ions, with LOD oxidized silicon substrates via cathode-ray spray. The nanoparticle layer
of 7.8 pM for Pb2+ and 5.4 pM for Hg2+, and an analytical range of was functionalized with DNAzymes that self-cleave in the presence of
0.01–100 nM, as measured by EIS at 0.2 V [196]. Later, Zhou et al. re- Pb2+. This device was demonstrated as an environmental sensor for
ported a new label-free impedimetric detection system based on DNA- detecting Pb2+ at concentrations as low as 10 nM [198]. Zhang et al.
zymes and ordered mesoporous gold-carbon nanoparticles (OMC-GNP) developed a method using an electrically heated indium tin oxide (ITO)

Fig. 11. Schematization of electrochemical sensor based on MOFs composites, gold nanoparticles, and DNAzyme for Cu2+ sensitive detection [204].

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H. Abd El-Raheem et al. Microchemical Journal 207 (2024) 112086

electrode. A double-stranded Y-shaped DNA (DNAdb) was formed by nanomaterials, as well as biomolecules like aptamers, oligonucleotides,
hybridizing a DNAzyme, substrate, and capture DNA, and Ru(phen)32+ peptides, DNA/DNAzymes, and aptamers. Nanomaterials are exten-
was integrated into the DNAdb groove as an electrochemiluminescence sively used due to their unique properties, including high catalytic ac-
(ECL) indicator. The ECL signal showed a linear relationship with the tivity, strong adsorption capabilities, and a large surface area-to-volume
logarithmic concentration of Pb2+ (0.25 to 500 pM), with a LOD of 0.2 ratio, which make them ideal for integration with electrochemical
pM at an electrode temperature of 45 ◦ C, which was approximately five techniques. This combination results in fast reaction times, high sensi-
times more sensitive than at 25 ◦ C [199]. tivity, and the ability to detect multiple analytes at low detection limits.
Weng et al. proposed a highly sensitive electrochemical biosensor for This review also explores various types of interface materials, such as
Pb2+ using a dual-amplification strategy. Pb2+ and the DNAzyme (S2) noble metal nanoparticles, carbon-based materials, and aptamers, used
were continuously involved in cutting the substrate strand (S1), leading to modify conventional electrodes like screen-printed, glassy carbon,
to a decrease in the electrochemical signal. Long-chain double-stranded and graphite electrodes for the detection of HMIs. Nevertheless,
DNA (dsDNA) was formed by hybridization chain reaction (HCR), and simplifying the design and techniques for electrochemical measure-
methylene blue was adsorbed on the long dsDNA to produce the elec- ments of HMIs, as well as miniaturizing electrochemical sensors, re-
trochemical signal. The sensor showed a linear response to Pb2+ con- mains a significant challenge. Future studies should focus on developing
centrations ranging from 50 pM to 1 μM, with a LOD of 15 pM [183]. In portable, high-throughput instruments capable of detecting multiple
2020, Duong et al. developed a sensor based on the liquid crystal (LC) HMIs simultaneously, including universal probes and multichannel
droplet model for detecting Pb2+ in PBS. When Pb2+ was present, it paper chips. Additionally, it is crucial to continue advancing nano-
bound to the DNAzyme, releasing tetradecyltrimethylammonium bro- sensors for the detection and removal of HMIs. As technology pro-
mide (OTAB). OTAB molecules were absorbed at the water-LC interface, gresses, the number of nanosensors for HMI detection is expected to rise
altering the LC orientation. This caused a transition in the LC droplets, significantly, benefiting disease diagnosis, food safety, and environ-
observable by the naked eye, with a LOD of 0.7 nM in PBS and 0.8 nM in mental monitoring.
tap water, Fig. 9 [200].
Liu et al. (2021) developed a novel electrochemical biosensor for CRediT authorship contribution statement
detecting Pb2+ by targeting the Pb-adenine (rA) site in the DNA sub-
strate strand, leading to the splitting of the double helix. This enhances Hany Abd El-Raheem: Writing – original draft, Visualization,
the adsorption capacity of Ti3C2Tx-Mxene toward GR5 DNAzyme, Validation, Conceptualization. Rabiaa Helim: Writing – review &
promoting ion incorporation into Ti3C2Tx-Mxene and increasing the editing, Validation. Rabeay Y.A. Hassan: Writing – review & editing,
oxidation peak current. The GR5 DNAzyme/Ti3C2Tx Mxene-GCE suc- Visualization, Validation, Methodology, Data curation, Conceptualiza-
cessfully detected Pb2+ with a linear range of 0.5–32 nM and a LOD of tion. Ahmed F.A. Youssef: . H. Korri-Youssoufi: Writing – review &
0.1 nM [201]. In 2022, Liu et al. utilized thymine, a building block in editing, Visualization, Validation, Conceptualization. Charoenkwan
DNA, which has a specific binding affinity for Hg2+, forming a metal- Kraiya: Validation, Supervision, Conceptualization.
mediated base-pairing complex (thymine-Hg2+-thymine). Thymine-
containing DNA sensors have been widely studied due to their specific
Hg2+ binding sites and easily detectable optical signals. Liu et al. Declaration of competing interest
developed an allosteric DNAzyme with varying numbers of thymine-
thymine pairs to detect Hg2+, achieving a LOD of 2.4 nM [202]. A The authors declare that they have no known competing financial
more recent approach combines SERS with nucleic acid rolling circle interests or personal relationships that could have appeared to influence
amplification (RCA) for the trace detection of Pb2+ Fig. 10. Lead ions the work reported in this paper.
selectively bind to a Pb2+-dependent DNAzyme, facilitating efficient
substrate cleavage. Utilizing RCA and SERS with biological barcoding Acknowledgments
techniques, this method achieves highly sensitive detection of Pb2+,
with a LOD of 0.03 fM and a linear detection range of 0.1 fM–2 pM Hany Abd El-Raheem and Charoenkwan Kraiya would like to thank
[203]. the Second Century Fund (C2F), Chulalongkorn University, Thailand,
In a recent study by Sun et al. 2023, a novel electrochemical DNA for the support.
sensor was developed using Fe-MIL-101 as a substrate modifier and
electrochemically deposited AuNPs. DNAzyme was employed as a probe Appendix A. Supplementary data
for the specific detection of Cu2+ Fig. 11. DPV was used to measure Cu2+
concentrations. Optimal conditions included a DNAzyme concentration Supplementary data to this article can be found online at https://doi.
of 1 μmol, an incubation time of 5 min, a fixation time of 16 h, and a org/10.1016/j.microc.2024.112086.
reaction time of 30 min. Under these conditions, the sensor demon-
strated a detection range of 0.05 nM–50 µM, with a LOD of 1 pM [204]. Data availability

7. Conclusion and future perspectives No data was used for the research described in the article.

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