Trends in Environmental Analytical Chemistry 13 (2017) 1023

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Trends in Environmental Analytical Chemistry

journal homepage: www.elsevier.com/locate/teac

Nanomaterials based electrochemical sensor and biosensor platforms

for environmental applications
Govindhan Maduraiveerana,* , Wei Jinb,*
a
Department of Chemistry, Lakehead University, Thunder Bay, Ontario P7B 5E1, Canada
b
National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Key Laboratory of Green Process and Engineering, Institute of
Process Engineering, Chinese Academy of Sciences, Beijing 100190, China

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

Article history:
Received 15 February 2017 A wide range of toxic chemicals is currently released into the environmental in terms of airborne, aquatic
Received in revised form 16 February 2017 and solid wastes due to the rapid international globalization and industrialization. Thus, a sensitive,
Accepted 17 February 2017 reliable and cost-effective sensor platform for emerging environmental pollutants is of great importance.
The considerable advancements have been made on the successful electrochemical sensor and biosensor
Keywords: platforms based on nanomaterials for environmental applications. In the present review, the recent
Nanomaterial trends in the development of the electrochemical sensor platforms based on state-of-the-art
Modied electrode nanomaterials such as metal nanoparticles, metal oxide nanomaterials, carbon nanomaterials, polymer
Electrochemical sensor
and biomaterials are assessed. The unique synthetic approaches, properties, integration strategies,
Environmental monitoring
selected sensing applications and future prospects of these nanostructured materials for the design of
Food safety
advanced sensor platforms are also highlighted. The signicant development of the nanomaterials based
electrochemical sensor platforms is giving rise to new impetus of generating novel technologies for
securing the human and environmental safety.
2017 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2. Synthesis and properties of nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3. Noble metal nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.1. Gold nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.2. Silver nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.3. Platinum nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
3.4. Palladium nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4. Metal oxide nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4.1. Metal oxides nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4.2. Metal oxides nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
5. Carbon nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
5.1. Carbon nanotubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
5.2. Graphene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
5.3. Porous carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
6. Polymer and bio-nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
6.1. Polymer nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
6.2. Bio-nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
7. Conclusions and future outlooks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21

* Corresponding authors.
E-mail addresses: mgovindh@lakeheadu.ca, pgmadura@yahoo.co.in (G. Maduraiveeran), wjin@ipe.ac.cn (W. Jin).

http://dx.doi.org/10.1016/j.teac.2017.02.001
2214-1588/ 2017 Elsevier B.V. All rights reserved.
 G. Maduraiveeran, W. Jin / Trends in Environmental Analytical Chemistry 13 (2017) 1023
1. Introduction
In recent years, the development of analytical methods based
on nanomaterials have made growing attention for numerous
applications, including the fundamental biological research,
monitoring of health, clinical diagnostics, pharmaceutical analysis,
food safety and environmental monitoring. Owing to their
exceptional physicochemical properties, high surface-to-volume
ratio, high adsorption and reactive capacity and other benecial
properties not present in the bulk materials, nanomaterials have
acted as potential analytical probe for not only offer enhanced
sensitivity but also provide a stair change to analysis the single
molecular realm [1]. Nanomaterials with unique functionalities
and practises create promising development of the novel analytical
systems that are easily triggered on exposure to emerging
chemical pollutants as well as real time environmental monitoring
in air, soil and water and food safety based on the essential to shield
the environment and public health [2]. The major group of
unregulated chemicals that can be classied majorly as heavy
metals, inorganic anions, phenolic compounds, pesticides and
chemical warfare reagents, which can cumulatively source severe
damage to human health and environmental. Some of the
pollutants are assumed of being cancer promoters and others
have been associated with endocrine disrupting effects via food
chain [3,4].
Over the recent decades, electrochemical sensor and biosensor
platforms with the integration of nanostructured materials have
tremendously been employed as powerful analytical methods by
captivating the benet of easy-to-handle, cost-effective, high
sensitive and selective, rapid response, facile-to-fabricate and
portable. Fig. 1 shows the schematic illustration of the nano-
material based electrochemical sensor and biosensor platform for
environmental and food safety applications. As displayed in Fig. 1, a
number of electrochemical analytical techniques such as ampero-
metric/potentiometric sensor, electrochemical impedance sensor,
electrochemical luminescence sensor and photoelectrochemical
sensor employ a wide range of chemical and biological analytes in
terms of change in electrode interfaces via electrochemical route
for numerous applications [5]. Diaz-Gonzalez et al. [6] recently
reviewed the overview of the electroanalytical tools that
Fig. 1. The schematic illustration of the nanomaterial based electrochemical sensor
and biosensor platforms for environmental applications.
11
successfully applied for the detection of environmental pollutants
recorded in the list of European Union (EU) set and other bodies.
The advanced analytical methods using the combination of
electrochemical devices in automatic uidic structures that
permitted the pre-conditioning sample and system standardisa-
tion is necessary for continuous environmental monitoring. These
electroanalytical techniques have been employed with numerous
sensor platforms wrapping a widespread range of nanomaterials
and the fabrication convolution. Due to the signicant realizations
in nanoscience and nanotechnology, the amplication of electro-
chemical signal based on advanced nanomaterials have had a great
prospective of enhancing both sensitivity and selectivity through
novel functions such as effective catalytic activity, fast electrode
kinetics, active large surface area, and control over the microenvi-
ronment of electrodes [7].
The structuring of the electrode surface at the nanoscale plays a
crucial part in the development of high-performance electrochem-
ical sensor platforms through numerous electrochemical funda-
mentals for the detection of target analytes [8]. The important
motivation of the design of the nanoscale electrode materials is not
only focus on the signal amplication via the catalytic activity and
conductivity, but also likely to provide facile interactions with
chemical and biological reagents and the immobilization of the
functional moieties with precisely designed as signal tags,
prominent to highly selective sensing [9]. Thus, the construction
of the functional nanoscale electrode materials is recently
advancing the wide environmental sensor applications. Besides
the advantages of the fabrication of functional nanocomposite
based sensor platforms, there are numerous characteristic draw-
backs, including mass transport and electron transfer may be
negatively impacted with functional and stabilization molecules
and the recurrent occurrence of dissolution and aggregation of
nanomaterials. The formation of nanocomposites or functional
nanocomposites directly grown on the electrode surface, which is a
promising resolution for the above discussed problems, as
proposed by Govindhan et al. [1012]. These necessary require-
ments should be instinctive while designing the electrode
materials. The growing of advanced nanomaterials based electro-
chemical sensor platforms establishes a very effective and robust
research eld that may be anticipated to offer next generation
electrochemical technologies for environmental analyses. A wide-
ranging effort has been made on the expansion of electrochemical
sensors and biosensors based on the functional nanostructured
electrode materials, united with various electroanalytical meth-
ods, evolving the extensive environmental applications [13,14].
This review mainly concentrates on the recent advances in the
development of nanostructured electrode materials based sensor
and biosensor platforms for the detection of emerging environ-
mental pollutants, which presents in the environment and food
materials in order to protect human and environmental health. The
present effort is to provide a perfect and brief vision of synthesis
and properties of advanced nanomaterials, construction and the
integration of the sensors based on nanomaterials. Furthermore,
we highlight the latest development of the improved electro-
chemical sensors and the perspectives related to environmental
applications rapidly emerging area may be taken in to consider-
ation in future design, which may inspire broader interests in
numerous area.
2. Synthesis and properties of nanomaterials
Owing to the numerous unique physical, chemical and
biological properties of the nanomaterials and their nanocompo-
sites, a signicant effort has been invested on the development of
the synthetic strategies with highly controllable size, shape,
surface charge and physicochemical characteristics over the last
12 G. Maduraiveeran, W. Jin / Trends in Environmental Analytical Chemistry 13 (2017) 1023
few decades [15]. Nanomaterials provide huge advantages on
various applications, catalysis, imaging, biotechnological and
sensor applications because of their improved properties. Three
main paths have been employed for the production of the
nanomaterials, including physical strategy (such as physical vapor
deposition and laser ablation), chemical strategy (such as chemical
vapor deposition, sol-gel processes, thermal decomposition and
hydrothermal method), electrochemical (such as anodic oxidation
and electrodeposition) and photochemical strategy (such as photo-
deposition) [16]. The integrations of the dimensional, composi-
tional, geometric and structural properties of nanomaterials are
vital to convey unique functionality and properties of the
nanomaterials. The adsorption and interaction of the nano-
materials with chemical or biomolecules are key signicant on
the fabrication of nanomaterials for catalysis and sensor applica-
tions [17]. Several research groups have involved to address
numerous concerns on the development of the nanomaterials for
electrochemical sensor applications. The controlled size and
composition, interfaces and distributions, nucleation and growth,
stability, scale-up synthesis and assembly strategies for low-cost,
large-scale production are main concerns of the synthesis of the
nanomaterials [18]. There are numerous nanomaterials and their
nanocomposites have employed for the environmental sensor
applications because of the various attractive characteristics,
including high chemical (bio) compatibility and inertness, easy to
functionalize, huge surface energy and great electrode kinetics
[19].
The high surface area to volume ratio of the nanomaterials
allows enhanced catalytic and sensing response by the rapid
movement of analytes through nanomaterials based electrodes or
sensors. The excellent optical, magnetic, electrical and catalytic
properties signify the prots over the macroscale materials,
revealing the notable specic properties [20]. The physical and
catalytic properties of the nanomaterials can be easily tuned or
altered by the reduction of the spatial dimension or the
connement of the structures in a precise crystallographic
direction. In particular, the properties of the nanomaterials are
mainly associated to different origins via large fraction of surface
atoms, large surface energy, spatial connement, and the reduced
imperfections. These can be tuned simply by adjusting the size,
shape or extent of agglomeration [21]. Due to the enormous
fraction of surface atoms in the total amount of atoms, nano-
materials possesses lower melting point and reduced lattice
constants. The reduction of the materials dimension has obvious
effects on the optical properties and the size and structure
dependence can be categorized into surface plasmon resonance
(SPR) and the quantum size effects [22]. The electrical conductivity
decreases by increased surface scattering. The mechanism of
electrical conductivity on the thin lm can be extensively
explained by a simple tunneling between localized insulating
states, which imply a high resistivity at low temperatures[23]. For
the catalytic property of the nanomaterials, geometry, composi-
tion, oxidation state, and chemical/physical environment can play
a vital role in determining catalytic activity and reactivity of the
nanomaterials, while particle size and shape is an important
consideration. Thus, the relationship between these parameters
and the catalytic performance of the nanomaterials may be system
dependent. Moreover, a systematic understanding of the factor
that control catalyst reactivity and selectivity is a vital [17,24].
3. Noble metal nanomaterials
Owing to the unique size and shape dependent physical,
chemical and electrochemical properties of the noble metallic
nanomaterials such as gold (Au), silver (Ag), platinum (Pt),
palladium (Pd) and their bimetallic alloys and core-shell
nanoparticles are predominantly fascinated for numerous envi-
ronmental applications [25,26]. Metal nanoparticles play various
key roles in the design of the electrochemical sensor and biosensor
platforms through a facile synthesis, ease of surface functionaliza-
tion, stress-free sensor fabrication approach, catalysis of electro-
chemical reactions and the enhancement of an electron transfer
process [27]. Recent years, metal nanoparticles based electro-
chemical sensor platforms provide a strong potential with
enhancing both sensitivity and selectivity via tuned signal
amplications. With recent advances on the design of the metal
nanoparticles, bio-functionalized nanoparticles and the effective
nanocomposites with matrices have attracted for sensor and
biosensor applications. The extensive research has led to the
development of advanced numerous analytical methods for
environmental monitoring and food safety applications.
3.1. Gold nanoparticles
Signicant efforts have been made on the development of the
electrochemical sensor and biosensor platforms based on Au
nanoparticles for environmental applications due to the unique
properties such as nely tunable optical properties, high surface
area and capacity for the surface modication. The Au nano-
particles have successfully employed as an effective electrocatalyst
in numerous electrochemical reactions because of their superior
stability and complete recovery in chemical redox processes. The
Au nanoparticles open the possibility for the miniaturization of
sensing devices to the nanometer scale, which offer excellent
chemical sensing prospects. Nanoscale electrochemical sensor
based on Au via micro- and nanofabriation technologies offer a
marvellous impending for the development of sensor array
platforms for the electrochemical detection of environmental
pollutants. In recent years, the integration capability of the sensor
arrays with microuidic devices provides possibilities for lab-on-a-
chip technology for the sensing of multiple analytes in a high-
throughput approach [28].
The use of Au nanoparticles based modied electrodes or
nanosized electrodes offers numerous advantages such as im-
proved diffusion of electroactive species, high selectivity, im-
proved catalytic activity and higher signal-to-noise ratio (S/N).
These properties are signicant in the development of a
nanostructured Au based electrode material for sensing analytes.
A facile electrochemical sensor platform for the detection of
arsenic ions (As3+) was developed based on Au nanoparticles by
Huang co-workers [29], where an electrochemical approach for the
characterization of the nanoscale effects of Au nanoparticles was
established for electroanalytical applications. This sensor offered a
simple and economical process for the fabrication of the electrode
materials, which showed a high 16.15 mA mM 1 and a low
detection limit of 32.5 pM. It is developed that the EDTA was
effectively employed to eliminate interference from several metal
ions. Mandler co-workers have reported that Au nanoparticles
modied electrode surfaces exhibited a high sensitivity and
sharper and more reproducible stripping peaks of mercury (Hg)
[30]. A low detection limit was attained to be 1 mM L 1 for Hg,
which was accomplished at the electrostatically adsorbed Au
nanoparticles on ITO. They found that Hg preferentially strips from
ITO rather than from Au and the presence of low amount of Au
improves the detection limit by serving as nucleation sites for its
deposition.
Nanoscale Au electrode material has been effectively employed
as an amplied signal carrier for the design of several sensor
platform. It is understood that the Au nanoparticles offer a
convenient and stable connection between carrier and biomole-
cules, carrying high electrochemical response into the detection
system. A sensor was established for the detection of mercuric ions
 G. Maduraiveeran, W. Jin / Trends in Environmental Analytical Chemistry 13 (2017) 1023
(Hg2+) with atto-molar detection limit (0.001 aM) [31]. Fig. 2 shows
the schematic representation of the electrochemical sensor
platform for the detection of Hg2+. Such a low detection limit
was mainly attained by the graphene-Au and the signal
amplication by nanoAu carrier strategy. For the selective and
sensitive detection of the Hg2+, three single-stranded DNA probes
were employed, which combined T-Hg2+-T coordination chemistry.
A simple, disposable dual electrochemical sensor was developed
for nitrate (NO3 ) and Hg2+ based on carbon print paper modied
with the combination of selenium (Se) and Au nanoparticles [32].
The selection of Se nanoparticles act as an absorbing agent for Hg2+
and the Au nanoparticles catalyze the reduction of NO3 and Hg2+.
The dual sensor exhibited an enhanced the sensitivity of NO3 and
Hg2+ with detection limits of 8.6 mM and1.0 ppb, respectively.
In order to improve the stability and reproducibility of the
sensor platform, much effort has been devoted to refresh the
surface of the sensor for the detection of environmental pollutants.
For instance, numerous methods such as vacuum annealing, laser
ablation, ame etching, chemical oxidative etching, and electro-
chemical polarization have been employed to refresh the surface of
the electrodes. However, these strategies easily lead to changes in
surface chemistry and the structure of the electrode, and thus
negatively affect the electron-transfer kinetics. Recently, Hu et al.
established an approach to clean the electrodes via UV or visible
light irradiation without affecting the activity of the electrodes. A
refreshable photo-electrochemical sensor platform was developed
for the detection of bisphenol A (BPA) based on Au nanoparticles
modied with carbon doped TiO2 nanotube arrays (NTAs) [33]. The
Fig. 2. The sensing approach for the sensitive detection of Hg2+is schematically illustrated. (Reprinted with permission from Ref. [31]). 2015 American Chemical Society.
13
developed sensor displayed an excellent electrochemical activity
and high sensitivity (2.8 mA mM 1 cm 2) with the detection limit
of 6.2 nM (S/N = 3) for BPA due to the combination of electro-
catalytic properties and photocatalytic activities.
3.2. Silver nanoparticles
Owing to the high conductivity, amplied electrochemical
signal and excellent biocompatibility, the development of the Ag
nanoparticles based sensor platform has made signicant impact
for environmental applications. Over last two decades, extensive
effort has been made towards the design of novel analytical
methods based on Ag nanoparticles and their nanocomposites for
food safety and environmental monitoring. It has been succeeded
that the Ag nanoparticles have recognised as one of the
outstanding groups of the nanomaterials for electrochemical
sensing and biosensing methods. Silver nanoparticles based
electrode materials have unlocked up the opportunity of generat-
ing new analytical platforms for emerging environmental organic,
inorganic and biological pollutants due to their high sensitive and
specic nature [34,35].
The incorporation of the Ag nanoparticles into numerous
matrixes such as metal oxides, silicate network, polymers,
graphene, bers, dendrimers, etc. provides enhanced sensing
performance with high stability because of the extended utility of
the materials. The sensitivity and stability of the sensor platform
relate to the dispersion and the prevention of the aggregation
process of the Ag nanoparticles in the network or matrices. Silver
14 G. Maduraiveeran, W. Jin / Trends in Environmental Analytical Chemistry 13 (2017) 1023
nanoparticles are stabilized via steric repulsion and electrostatic
repulsion of the stabilizing agents with polymers or other matrices.
For instance, Maduraiveeran et al. have developed an amperomet-
ric sensor platform based on Ag nanoparticle-silicate core-shell
nanoparticles for the detection of nitroaromatic compounds [36].
The resulted sensor exhibited an excellent activity towards the
sensing of nitroaromatics with a low detection limit of 5 nM. In
addition, the sensor was stable for over ve days with reproducible
results due to the nanoparticles immobilization in the amine
functionalized silicate network. Sadik co-workers have recently
demonstrated an electrochemical sensor platform based on Ag
nanoparticles embedded in the poly(amic) acid (PAA) polymer
matrix (PAA-Ag NPs) for nitrobenzene [37]. The PAAAg nano-
particles based sensor exhibited a detection limit of 1.68 mM with a
wide linear range of 10600 mM and a high sensitivity of
7.88 mA mM 1 with minimal interference effects on structurally-
similar nitroaromatic compounds.
A label-free electrochemical biosensor platform was estab-
lished with Ag nanoparticles on terminal deoxynucleotidyltrans-
ferase (TdT) extended ssDNA for the sensitive detection of Hg2+
[38]. The developed biosensor showed a high performance to Hg2+
sensing with a detection limit of 3 pM with good reproducibility
and high selectivity towards other interfering metal ions. The
developed simultaneous sensor for the detection of lead ions (Pb2
+
), cadmium ions (Cd2+) and copper ions (Cu2+) was developed
based on Ag nanoplates (Ag NPls) using a microuidic paper-based
analytical device (mPAD) coupled with dual electrochemical and
colorimetric methods [39]. The low detection limit was found to be
0.1 ng mL 1 for all metals. This simultaneous sensor was success-
fully tested real samples and they were quantied with ICP-OES
method, conrming the accuracy and reliability of the sensor. This
could be useful for food and environmental analysis. Interestingly,
Compton group recently developed a nano-electrochemical
technique for the rapid detection of single inuenza viruses
tagged with the Ag nanoparticles [35]. In this analytical method,
the Ag nanoparticles were adsorbed onto the surface of virus. The
current spikes were recorded with sufcient applied potential to a
carbon electrode, which related to the oxidation of the nano-
particles garnishing the virus. The current frequency and their
magnitude were linear proportion to the concentration of virus
and to the surface coverage of the nanoparticles, respectively.
Silver nanoparticles based electrochemical immunosensors
combine the merits electrochemical technology and immuno-
assays in terms of a rapid response, high sensitivity and specicity
and easy fabrication. They have attracted much attention for
monitoring numerous analytes, including small organic and
inorganic molecules, microorganisms, and virus. Zeng co-workers
recently have developed a sensitive electrochemical immunosen-
sor for the detection and determination of avian inuenza virus H7
(AIV H7) using Ag nanoparticle-graphene (Ag NPs-GR) as labels in
clinical immunoassays [40]. This sensor showed a low detection
limit of 1.6 pg mL 1 with a wide working range of 1.6 mg to
16 ng mL 1. The developed electrochemical assay may potentially
be employed to detect other pathogenic microorganisms.
3.3. Platinum nanoparticles
Over the last decade, Pt nanoparticles have attracted much
attention in the eld of electrochemical sensors for various
environmental applications because of their distinctive electronic
and electrocatalytic properties. The properties of the Pt nano-
particles can be easily inuenced through structure dependent
interatomic bond distances, chemical reactivity and electronic
properties. The electron-transfer process of the Pt nanoparticles
can be signicantly inuenced by chemical composition, surface
condition, crystal structure, crystallographic axis orientation and
other parameters. Platinum derived nanocomposites based elec-
trode materials in sensors is an effective method towards the
extension of their electronic and electrochemical properties [41].
Platinum nanoparticles based electrode materials can be
prepared via chemical reduction, metalvapor synthesis, electro-
chemical and photochemical deposition etc. The choice of the
strategy is also play a key role to develop the Pt nanoparticles on
the numerous electrode surface, which exhibits their superior
chemical inertness, good stability, low background current, high
catalytic and sensing performance [4145]. Einaga co-workers
have recently developed a sensor platform based on electrochem-
ically deposited Pt nanoparticles on a boron-doped diamond
surface (BDD) for the detection of hydrogen peroxide (H2O2) [43].
The electrochemical deposition approach is suitable to construct
the Pt nanoparticles on BDD electrode due to its simplicity and ease
of fabrication. The detection limit was found to be 100 nM with a
wide linear range of 0.0520 mM. Further this sensor was then
employed in immune-chromatographic strip test for melamine
detection.
Research effort has been already established based on the
application of microuidics, which has encouraged the develop-
ment of new analytical techniques for acting rapid analysis, high
resolution and sensitivity. Amatore group has developed the
analytical methods based on microchannel electrodes, which can
be used to understand the mass transport regimes and increase the
performance of the sensors [42]. The Pt-black coated Pt (Pt/Pt-
black) based electrodes were microfabricated for the sensitive
detection of H2O2 and nitrite (NO2 ) in PBS. The active surface area
of the Pt/Pt-black electrodes permitted to escape inhibition effect,
which led to perform the long term stability in contrast to the bare
Pt electrodes. The Pt/Pt-black electrodes based sensor showed the
detection limits of 10 and 12 nM for H2O2and NO2 respectively.
Platinum nanoparticles dispersed on graphene, mesoporous
silica microspheres, metal oxide nanomaterials, etc. have success-
fully developed for the enhanced sensing of emerging pollutants.
Hence, a design of novel composite nanomaterials is highly
desirable for the construction of the advanced electrochemical
sensors, in particular for nitroaromatic compounds. The PtPd
concave nanocubes dispersed on graphene nanoribbons (PtPd-rGO
NRs) were prepared via a hydrothermal process for the detection of
trinitrotoluene (TNT) by Zhang et al. [44]. The PtPd-rGO NRs based
sensor platform demonstrated a wide linear range from 0.01 to
3 ppm with a detection limit of 0.8 ppb for TNT. The electrochemi-
cal sensor for naphthol (NAP) isomers based on b-cyclodextrin
(b-CD)-Pt nanoparticles (Pt NPs)/graphene nanosheets (GNs)
nanohybrids (b-CD-PtNPs/GNs)[46]. This sensor showed a linear
response range of 0.8220 nM for a-NAP and 3300 nM for b-NAP,
with improved detection limits. Recently, Mahmoudian et al. have
developed a sensitive electrochemical sensor for Hg2+ using a
polypyrrole coated on nanospherical platinum (Pt/PPy NSs) [45].
The electrochemical sensor showed a linear range between 5
500 nM with a detection limit of 0.27 nM for Hg2+. It exhibited a
sensitivity of 1.239 mA nM 1 cm 2 with high selectivity from other
interferences from Ag+, Fe2+, Mn2+, K+, Pd2+, Cu2+, Ni2+, Pb2+, Sn2+
and Zn2+, presented a strong prospect for the detection of Hg2+.
3.4. Palladium nanoparticles
Palladium nanoparticles have attracted much more interest due
to their extensive catalytic and sensor applications towards gases,
biomolecules and hazardous toxic molecules. The Pd nanoparticle
based electrode materials exhibit high electrocatalytic activities
towards various analytes. The abundance of Pd over other noble
metals such as Au and Pd, which marks a cheaper substitute for
utilization in the designing of various electrochemical sensing
platforms. A diversity of Pd based nanomaterials, including of
 G. Maduraiveeran, W. Jin / Trends in Environmental Analytical Chemistry 13 (2017) 1023 15

metals, metal oxides and carbon nanomaterials with tailorable
structures and variable composition have been effectively applied
towards the detection of numerous pollutants due to their
attractive electronic properties and high catalytic activities. The
Pd based nanocomposites can improve the mass diffusion of the
analytes, which offered electron tunneling to enable the electron
transfer between the active site and the electrode, leading high
electrochemical sensing performance.
A facile sensitive and simultaneous electrochemical sensor
platform was developed for the detection of toxic metal ions using
of the Pd nanoparticles (Pd NPs) dispersed on porous activated
carbons (PACs) [47]. Due to the high porosities, high surface area
and large pore volumes, the PACs are effectively employed as solid
support for the dispersion of Pd nanoparticles, revealing the
advantageous for the applications as a sensor platform for the
detection of multiple Cd2+, Pb2+, Cu2+, and Hg2+ analytes with nano-
molar detection limits. As shown in Fig. 3, the developed
electrochemical sensor had demonstrated an excellent electro-
catalytic activity, selectivity, sensitivity and low detection limit for
detections of heavy metal ions even in a real milk sample. Owing to
a synergistic effect between the Pd nanoparticles and the PACs, the
sensor attained the improved electrochemical sensing perfor-
mance. Wei co-workers developed a simultaneous sensor for
ractopamine (RAC), salbutamol (SAL) and clenbuterol (CLB) based
on reduced graphene oxide (rGO) and Ag-Pd nanoparticles (AgPd
NPs) [48]. Some Europe countries set a strict regulation for these
molecules in animal foods as zero-tolerances. This multiplexed
sensor showed a linear range from 0.01 to 100 ng mL 1 with
detection limits of 1.52 pg mL 1, 1.44 mL 1 and 1.38 mL 1, respec-
tively. In this sensor platform, the AgPd nanoparticles offered a
strong electrochemical signal that can be employed to detect these
molecules with high sensitivities.
Palladium nanoparticles embedded with polypyrrole (PPy) is an
effective sensing electrode materials for a wide range of
applications in various elds of research because of their
outstanding properties. An electrochemical nitrate sensor was
developed based on Pd nanoclusters with PPy (Pd NCs-PPy) by
Silakhori et al. [49]. Differential pulse voltammetry (DPV) was
employed for the detection of NO3 in 0.1 M phosphate buffer (PB)
at pH 7. The Pd NCs-PPy based electrochemical sensor exhibited
two linear plots. The rst linear range increases from 100 to
800 mM, and the second linear range increases from 800 to
1400 mM. The low detection limit was found to be 0.45 mM. Sophia
et al. have developed an electrochemical H2O2 sensor based on the
Pd nanoparticles stabilized with polyvinylpyrrolidone (PVP) [50].
The vinyl polymers offer the capability to preserve the inherent
catalytic activity of the metal nanoparticles intact with the
chemical stability and the afnity of PVP vinyl polymer towards
the Pd metal. The resulted sensor platform showed a detection
limit of 8 nM with a wide range between 0.01 mM to 1 mM based on
the amperometric results.
4. Metal oxide nanomaterials
Metal oxides nanomaterials with large surface area, high
adsorptive capacity, unique electrochemical activity and stability
are of great importance for the design of electrochemical sensor
platforms [51]. The analytical performance of the metal oxide
nanomaterial based sensor can be well tuned by tailoring the
properties of the morphology, particle size, surface area and
surface functionality.

Fig. 3. (a) CVs of the bare, Pd1.0/PAC-900, and Pd1.5/PAC-900 electrodes in a mixture of 3.5 mM Cd2+, 3.2 mM Pb2+,6.0 mM Cu2+and 3.2 mM Hg2+. (b) DPV curves of the Pd1.5/PAC-
900 electrode recorded under different metal ion concentrations (0.58.9 mM) and (c) corresponding linear calibration plots. Electrolyte: 0.1 M ABS (pH 5.0); Scan rate:
50 mV s 1. (d) Similar to (b) but in the presence of a mixture of a real milksample with metal ion analytes: 2.4 mM Cd2+, 2.9 mM Pb2+, 2.9 mM Cu2+and varied amounts of Hg2+
(1020 mM). Electrolyte: 5 mL of milk extract with 5 mL of ABS (pH = 5). (Reprinted with permission from Ref. [47]). 2016 American Chemical Society.
16 G. Maduraiveeran, W. Jin / Trends in Environmental Analytical Chemistry 13 (2017) 1023
4.1. Metal oxides nanoparticles
For the synthesis of nanostructured metal oxides, chemical
methods comprise reduction of metal ions and controlled
separation of the formed metal atoms from the bulk solution.
They are quite favourable to obtain uniform nanoparticles such as
nanorods, nanobers, nanobelt, nanocomb and nanotubes. This
family of one dimensional (1D) nanostructures provide a great
model system for electrochemical sensing of environmental
pollutants. Resistive (conductometric) gas sensors based on
nanoscale metal oxide semiconductors such as SnO2, In2O3, ZnO,
TiO2, WO3 and NiO play an important role in the environmental
monitoring of explosive/toxic gases and volatile organic com-
pounds (VOCs). The operating principle of resistive gas sensor is
based on the variation of resistance (electrical conductivity)
caused by the change of test gas molecules on the electrodes
surface. In order to improve the sensitivity and detection limit,
considerable efforts have been conducted on the design and
controllable synthesis of the hierarchical metal oxides nano-
structures due to their smaller size and characteristic charge
carriers [52,53]. SnO2 nanoparticle is one of the most applied
sensing materials for gas sensors.
Recently, Tyagi [54] has reported a hazardous sulfur dioxide
(SO2) gas sensor using SnO2 thin lm integrated with various
nanosctuctured metal oxides (PdO, CuO, NiO, MgO, V2O5). It has
been demonstrated the bare SnO2 thin lm sensor exhibited the
sensing response of about 1.3 at 220  C whereas, while NiO/SnO2
sensor presented an enhanced sensing response (56) towards
500 ppm SO2 gas at a low temperature of 180  C, as shown in Fig. 4.
Fig. 4. Schematic of the NiO/SnO2 metal oxide sensor (upper) and its transient
response towards SO2 gas at 180  C (lower). (Reprinted with permission from Ref.
[54]). 2016 Elsevier.
Khong et al. [55] have designed a hierarchical SnO2/ZnO
nanostructure for scalable preparation of the high-performance
volatile ethanol sensors. First, high-quality single crystalline SnO2
nanowire (NW) backbones were fabricated via the thermal
evaporation approach, subsequently ZnO nanorod (NR) branches
were vertically grown to the axis of SnO2 NWs via the
hydrothermal method. As compared to the bare SnO2 NWs sensor,
the hierarchical nanostructures exhibited improved ethanol gas
response and better selectivity for interfering gases such as NH3,
CO, H2, and CO2.
4.2. Metal oxides nanocomposites
On the other hand, the metal oxide can also be incorporated to
nanocomposite for environmental sensing from the view of
electrocatalysis. Kumar et al. [56] have developed a direct robust
As(III) sensor using zirconia nanocubes modied gold electrode.
Based upon the electrochemical oxidation behaviour of As, the
sensing was achieved by cyclic voltammetry (CV) and chronoam-
perometry (CA) with an ultra-sensitivity of 550 nA cm 2 ppb 1, a
detection limit of 5 ppb, and a wide linear range of 560 ppb with a
response time of <2 sand is presented in Fig. 5. Huang et al. [57]
have reported the combination of SnO2 and reduced graphene
oxide (rGO) for the simultaneous and selective electrochemical
determination of ultra-trace heavy metal ions in drinking water.
Square wave anodic stripping voltammetry (SWASV) has been
employed. The detection limit of 0.15 nM, 0.18 nM, 0.23 nM, and
0.27 nM were obtained towards Cd2+, Pb2+, Cu2+ and Hg2+,
respectively, well satisfying the guideline value of the World
Health Organization (WHO). Similarly, Wang et al. [58] have
demonstrated a three-dimensional nanocomposite of rGO and Cu/
Cu2O nanocrystal (3D Cu/Cu2O@rGO) for detecting poisonous
ractopamine (RAC), which was used illegally as feed additive for
growth promotion in farm animals. As compared to pristine Cu2O
nanospheres and porous rGO, ractopamine antibody (RACanti)
tends to anchor onto the surface of 3D multi-functionalized Cu/
Cu2O@rGO nanocomposite, leading to more sensitive RAC detec-
tion with a low detection limit of 7.5 pg mL 1 and linear range of
0.1 ng mL 1 to 10.0 ng mL 1. The interference from other co-
existing lean meat powders, urine components, and metal ions
can be effectively eliminated.
Ionic liquids (ILs) are novel molten salts with the melting point
close to or below room temperature, which comprise two
asymmetrical ions of opposite charges [59]. The high conductivity,
non-volatility and large electrochemical window make ILs
promising for many electrochemical sensors applications. Gao
et al. [60] developed a disposable As3+ detection platform by
Fig. 5. Schematic of arsenic detection at the zirconia nanocubes sensing platform.
(Reprinted with permission from Ref. [56]) 2016 Royal Society of Chemistry.
 G. Maduraiveeran, W. Jin / Trends in Environmental Analytical Chemistry 13 (2017) 1023
integrating the high adsorptivity of Fe3O4 microspheres and the
advantages of room temperature ionic liquid (RTIL). The Fe3O4-
RTIL nanocomposite modied screen-printed carbon electrode
(SPCE) offered even better performance than commonly used
noble metals, particularly with a high sensitivity of 4.91 mA ppb 1.
Nanoscale metal oxide-based electrochemical sensors present a
new protocol for the environmental monitoring.
5. Carbon nanomaterials
Carbonaceous materials exhibit excellent properties such as
good conductivity, high stability, low cost, wide potential windows
and easy surface functionalization [61]. Therefore, they have been
widely designed and employed for various electroanalytical
applications, particularly the emerged nanoscale carbon materials
families of carbon nanotubes (CNTs), graphene and nano/
mesoporous carbon. Their nanostructures enable favourable
exposure of surface groups for the binding between analyte
molecules and transduction material, leading to remarkable
detection performance for environmental pollutants [62,63].
5.1. Carbon nanotubes
As one of the most commonly used building blocks of
nanomaterials, carbon nanotubes have gained considerable
attention since its discovery in 1991. CNTs can be visualized as
cylindrical tubes rolled up from sp2 hybridized graphene sheets,
exhibiting 100 times tensile strength of steel, similar electrical
conductivity to copper, and excellent electrocatalytic ability. They
are classied into two types of single-walled carbon nanotubes
(SWNTs) and multi-walled carbon nanotubes (MWNTs), depend-
ing on single and multilayer graphene existed in the rolling
honeycomb structures. Several methods have been developed to
prepare CNTs [64], including chemical vapor deposition (CVD),
electrical arc discharge and laser vaporization. It should be noted
that the CVD is the most widely used commercial preparation
approach, resulting from the thermal decomposition of hydrocar-
bon vapor (e.g., methane) in the presence of a metal catalyst. CVD is
a simple, versatile and economic technique for CNTs fabrication,
while it needs careful product purication to remove residual
metals.
Due to the unique properties of large surface area, fast charge
transfers as well as the compatibility and synergistic effect with
the other electrode materials, many CNTs based environmental
sensors have been developed, including composite, pastes, lm,
and functionalised CNT electrodes. Maduraiveeran et al. [65] have
reported a single-walled carbon nanotube modied electrode for
the simultaneous selective detection and determination of the
toxic phenolic compounds (catechol, p-cresol and p-nitrophenol),
which are widely present in aqueous and biological systems. This
mediator-freesensor exhibited high sensitivity, good reproducibil-
ity and stability. Interestingly, Gooding et al. [66] have demon-
strated the electroanalytical performance of individual SWNTs is
more efcient than the corresponding MWNTs. The electron
transfer rate is largely determined by the amount of surface oxides
on the nanotubes that are exposed to the reactant. For the SWNT
based electrodes, the oxygen-functionalized carbon nanotube is in
direct contact with the solution, resulting in a fast electron transfer
and excellent electrochemical detection. However, the reactions
with MWNTs have been performed predominantly with nanotubes
in the non-oriented style and the sidewalls were mainly presented
to the solution, frustrating the charge transport and detection.
In order to further improve the electrochemical performance,
many efforts have been conducted on the modication and
integration of the carbon nanotubes. Zhao et al. [67] developed a
polyamidosulfonicacid (PASA) lm modied MWNTs for the
17
determination of hydroquinone and catechol. Due to the electro-
rich N atoms and high SO3 electron density in the polymer lm,
the response current at PASA/MWNTs/GC electrode is nearly two
times higher than the sum of peak currents at the PASA/GC and
MWNTs/GC electrodes. It is indicated that PASA/MWNTs compos-
ite lm can act as an efcient mediator to improve the kinetics of
the electrochemical reactions, resulting from the synergistic effect
between the PASA and MWNTs.
5.2. Graphene
Graphene is an emerged two-dimensional (2-D) nanomaterial
of sp2 hybridized carbon sheet assembled in a honeycomb lattice,
resulting in an extremely high surface area (theoretically
2630 m2 g 1, almost twice as that of SWCNTs). Besides, it is a
semiconductor with a zero band-gap, exhibiting ambipolar electric
eld effect with high charge carrier mobility (15,00020,000 cm2/
Vs). Furthermore, graphene also possesses superior mechanical
and thermal characteristics. Obviously, these excellent physico-
chemical and electrical properties enable graphene an exciting
attractive candidate for the fabrication of electrochemical sensor
electrode.
Graphene was rst isolated in 2004 via facile scotch-tape
exfoliation of highly oriented pyrolytic graphite (HOPG) [61].
Recently, many scalable, cost-effective and high-yield production
processes have been developed, such as the rGO (Hummers
method), electrochemical reduction, and chemical vapor deposi-
tion (CVD) [68,69]. It has been demonstrated that mechanical
exfoliation can generate graphene with basal planes structures,
high conductivities but decreased electrochemical activities, while
the methods involving chemical oxidations and reduction can
produce high electrochemical activity due to the increasing defects
and functional groups. Besides, the inevitable metal contamination
in the CVD method can contribute to the electrochemical
behaviour of nal product, addressing the necessity of accurate
metal species control during the fabrication process [70].
As discussed earlier, the geometry and electrochemical
properties of graphene makes it ideal transduction materials for
environmental sensing. Goh et al. [71] have developed the
graphene nanoribbons-based electrodes toward the sensitive
electrochemical detection of explosive 2, 4, 6-trinitrotoluene
(TNT), which is a common environmental ticking bombs in
seawater. The limit of detection of TNT in untreated seawater was
1 mg mL 1. Luo et al. [72] have reported a convenient electroana-
lytical detection of carcinogenic hydrazine and nitrite by syner-
getic grapheme-cobalt hexacyanoferrate nanocomposite, resulting
in the reduced oxidation overpotentials and increased current
response of the target analytes. The analytical platform was also
well demonstrated by the evaluation of water samples and pickled
food, in which the average recovery was found to be >92.2%.
Furthermore, graphene-based nanomaterials have been also
successfully employed in the monitoring of gaseous pollutants and
heavy metal contaminants. Li et al. [73] have fabricated graphene-
based devices via alternating current dielectrophoresis (ac-DEP)
for nitric oxide (NO) gas determination. The as-prepared device is
consisted of the sensitive channels of Pd-decorated rGO (Pd-RGO)
and the chemical vapor deposition (CVD)-grown grapheme
electrodes. As a result, highly sensitive, reusable and reliable NO
detection ranging from 2 to 420 ppb with response time of 700 s
has been obtained at room temperature. Dai et al. [74] have
developed an electrochemical sensor based on functionalized
polypyrrole (PPy)/GO for the detection of heavy metal ions. The
PPy/GO nanocomposites were fabricated by in-situ chemical
oxidation polymerization and electrostatic functionalization,
exhibited high electrochemical conductivity and remarkable
current increase as compared to PPy/GO and PA/GO modied
18 G. Maduraiveeran, W. Jin / Trends in Environmental Analytical Chemistry 13 (2017) 1023
electrodes. This modied electrode employed to measure Cd2+ and
Pb2+ with a wide linear working range of 5150 mg L 1, as
presented in Fig. 6.
5.3. Porous carbon
Porous carbon with a high surface area, accessible surface
chemistry, and short pathway for mass and electron transfer has
attracted considerable attention due to the promising applications
in electrochemical sensors. According to the International Union of
Pure and Applied Chemistry (IUPAC) recommendation, porous
carbon materials can be grouped into three classications based
upon their pore sizes: microporous <2 nm, 2 nm <mesoporous
<50 nm, and macroporous >50 nm [75]. Ma et al. [76] have
developed a sensitive electrochemical nitrobenzene (NB) sensor
based on macro-/meso-porous carbon materials, which were
fabricated by pyrolysis of the ionic liquid([AEIm]BF4) polymer (PIL)
pre-wrapped onto SiO2 microspheres and then removal of the
silica core. Owing to the large specic surface area and
accumulation effect in this porous structure, the MMPCMs
modied electrode presents stable, reproducible analytical perfor-
mance for NB detection with a linear response range of 0.240 mM
and the detection limit of 8 nM. Niu et al. [77] have reported a
bismuth porous carbon nanocomposite based screen-printed
electrodes (SPEs) for the heavy metal detection. The nano-
composite was synthesized by a combined one-step sol-gel and
pyrolysis process, followed by the milling down to a specic
particle size distribution for the screen printing ink. The resulting
electrodes were successfully applied to the detection of Pb2+ and
Cd2+ ions at concentration levels below 4 ppb in tap drinking water
and wastewater systems.
Recently, biomass-derived porous carbon is of great interest
because it can be readily prepared from the carbonization of low
cost precursors. Wang et al. [78] have proposed a three-
dimensional (3D) macroporous carbon (3D-KSCs) derived from
kenaf stem (KS) as a novel supporting material for electrochemical
sensing platform. The integrated cobalt nanoparticles/3D-KSCs
nanocomposite electrode shows a 3D honeycomb porous struc-
ture, exhibiting good electrocatalytic performances toward the
oxidation and detection of amino acid. Therefore, a linear range
from 0.10 to 18.60 mM with a sensitivity of 32.11 mA cm 2 mM 1
and a low detection limit of 0.05 mM was obtained for the N-acetyl
cysteine sensor. A linear range from 0.15 to 26.24 mM with a
sensitivity of 42.24 mA cm 2 mM 1 and a low detection limit of
0.02 mM were achieved for the detection of cysteine. Similarly,
Veerakumar et al. [79] have reported the palladium nanoparticles
(Pd NPs) on porous activated carbons (PACs) electrodes for the
Fig. 6. (a) Electrochemical behaviour and (b) corresponding calibration plots of PA/ppy/GO electrodes for the simultaneous detection of Cd2+and Pb2+. (Reprinted with
permission from Ref. [74]). 2016 Elsevier.
detection of toxic metal ions. The PACs were derived from waste
biomass feedstock (fruit peels), possessing desirable textural
properties and favourable porosities for the uniform dispersion
of Pd nanoparticles (ca. 34 nm). The Pd/PAC modied electrodes
showed superior performances for the individual and simulta-
neous detection of toxic heavy metal ions of Cd2+, Pb2+, Cu2+, and
Hg2+.
6. Polymer and bio-nanomaterials
Polymer and bio-nanomaterials based electrochemical sensor
and biosensor platforms offer improved sensitivity with rapid
response and selectivity due their radiant, electrical, catalytic,
mechanical, thermal and physical properties [80]. With increasing
the structural and functional complexity of polymeric and
biomaterials, it is very difcult to envisage the desired sensing
properties. The design and the development of the electrochemical
sensor platforms for detecting emerging environmental pollutants
based on polymeric and bio-nanomaterials with unique function-
alities and properties can be presently accomplished by combining
the novel analytical and scientic methods, including of combina-
torial and high-throughput materials screening with micro- and
nanofabrication and microuidics [81].
6.1. Polymer nanomaterials
Effort on the development of polymeric nanomaterials,
including homo- and copolymers, formulated materials, polymeric
structures with engineered morphology, and molecular shape-
recognition materials have been established for the sensitive
sensing of food and environmental pollutants [82]. With unique
properties, polymeric nanomaterials deliver a desirable variety in
electrochemical analytical strategies for the detection and
determination of the chemically and biological toxic analytes in
gases and liquids for numerous health and environmental
applications [83]. The polymeric nanomaterials based sensor
platforms have exhibited several properties, including intrinsic
properties of sensitivity, linearity, selectivity and the ease of
manufacturability. The formation of self-assembled bio-mem-
branes, electro-polymerized polymers (conducting polymers, CPs)
and dendrimers based polymeric nanomaterials have motivated
extensive devotion in the design of sensor platforms. Further
improve their electrochemical sensing properties, the fabrication
of the nanocomposites with metal nanoparticles, metal oxide
nanoparticles, (carbon nanotube) CNT and graphene [84,85]. With
highlighting the important achievements in design of sensor
platforms, the combination of the matrix and nanoller
 G. Maduraiveeran, W. Jin / Trends in Environmental Analytical Chemistry 13 (2017) 1023
Fig. 7. The preparation of the coreshell Fe3O4/Au nanocomposites and the process
for the electrochemical oxidative desorption of Thiocholine (A), the measurement
of the AChE activity through the reactivation from OP-exposed sample (B), the
parallel measurement of AChE activity in postexposure sample with and without
reactivation (C). (Reprinted with permission from Ref. [95]). 2013American
Chemical Society.
contributions are pronounced to enhance the biocompatibility,
excellent sensitivity and selectivity.
The polyaniline (PANI) nanobers modied with bentonite
nanohybrid was employed for gas sensor application towards toxic
gases such as acetone, benzene, ethanol and toluene [86]. It was
found the sensitivity of the developed sensor to the analyte gases
followed the following order: acetone > benzene > toluene > etha-
nol. The selectivity of the developed sensor was ascribed to two
factors including (i) the effect of vapor pressure of the gas analytes,
and (ii) the formation of dipolar, and p-electron delocalization
interactions between the nanohybrid and the gas analytes. Navale
et al. have developed the gas sensing properties of polypyrrole
(PPy)/a-Fe2O3 nanocomposites various oxidizing (NO2 and Cl2)
and the reducing (CH3OH, C2H5OH, H2S and NH3) gases at room
temperature [87]. The developed gas sensor showed a fast
response, stability and shorter recovery times as compared to
PPy, revealed the excellent gas sensing properties at room
temperature, which can be used as high performance selective
NO2 gas sensors. Recently, Lee et al. have developed an sensor
platform for hydrazine (N2H4) using poly(dopamine) (pDA)-
modied indium tin oxide (ITO) electrode [88]. CV technique
19
was employed to study the electrocatalytic oxidation of N2H4. The
pDA based sensing electrode acts as a mediator for the
electrochemical reaction, which exhibited good performance
towards the detection of N2H4. The prepared sensor displayed a
linear range from 100 mM to 10 mM with a detection limit 1 mM.
The molecular imprinting ploymers (MIP) is a division of
polymeric nanomaterials, which are effective approach for high
selective detection of molecules through articial recognition. This
is a straight-forward strategy to enable analytical chemists to
produce synthetic polymers, which are selective towards a
specied template through complementary non-covalent binding
sites. This is mainly based on ionic, hydrophobic or hydrogen bond
interactions [89]. The MIPs based electrochemical sensors can be
employed for the detection of a wide range of analytes, including
drugs, pesticides, peptides, sugars, organic compounds, viruses,
erythrocytes and immunoglobulin. Pingarron co-workers have
established a biosensor based on the nanocomposites of electro-
polymerized network of polyamidoamine dendrimer-coated Au
nanoparticles for the amperometric sensing of catechol in 0.1 M PB
(pH 7.0) [84]. The prepared biosensor showed a detection of 20 nM
with a wide linear range of 50 nM10 mM. In addition, the
biosensor was stable over 30 days when the sensor was kept at
4  C. This can be ascribed to the glutaraldehyde-mediated multi-
point attachment of the enzyme to the primary amino groups at
the surface of the poly(amidoamine) (PAMAM) hyper-branched
structures capping the Au nanoparticles-polymers network.
Another electrochemical immunosensor was developed based
on the antigenantibody immune reaction using single-walled
carbon nanohorns (SWCNHs)hollow Pt nanospheres/dendrimer
for procalcitonin (PCT) [90]. The combination of high specic
surface area of SWCNHs and the catalytically active Pt nano-
particles were comprised in the biosensor. The PAMAM dendrimer
was used to increase the quantity of the electrochemically active
compound thionine immobilized on the surface, which offered a
diamine core and an amidoamine branching structure. This
biosensor exhibited the high sensitivity, improved stability and
ideal selectivity with a wide linear response from 10 pg mL 1 to
20 ng mL 1. The limit of detection was found to be 1.74 pg mL 1,
revealed that this immunosensor might offered a new option for
clinical septicemia diagnosis through PCT detection.
6.2. Bio-nanomaterials
The integration of the biomolecules with nanoscale objects
provide numerous platforms which combine the characteristics of
the nanomaterials and catalytic function of biomolecules. A well-
dened nanostructure with biomaterials can be obtained by the
self-organization of biological molecules. These bio-nanomaterials
inspire the analytical researchers for biomedical and environmen-
tal applications [91]. On the development of advanced electro-
chemical sensor platforms, great efforts have been made with a
new generation of composite of nanostructured materials, which
emerge the sensor eld in the frontier between materials science,
life science, and nanotechnology. The bio-nanomaterials become
to elect nanocomposites, which involve enzymes, antibodies
(antigens), or DNA and a naturally occurring polymer (biopolymer)
in the arrangement with an inorganic moiety at least one
dimension on the nanometer scale. Due to the unique recognition,
transport, electronic and catalytic properties, the bio-nanomate-
rials offer highly selective catalytic and recognition properties of
biomaterials, such as proteins/enzymes, nucleic acids, biopoly-
mers, etc. Biomaterials consist of biomolecules, which are
attractive macromolecular structures in terms of their unique
recognition, transport, electronic and catalytic properties. A
numerous electrochemical sensor platforms have developed based
20 G. Maduraiveeran, W. Jin / Trends in Environmental Analytical Chemistry 13 (2017) 1023

Table 1
List of selected nanomaterial based electrochemical sensor and biosensor platforms for environmental applications.

Materials Pollutants Detection limit Linear range Ref.

Au NPs As3+ 32.5 pM 1.3200 nM [29]
Au NPs Hg 1 mM L 1 [30]
Au-Graphene Hg2+ 0.001 aM 1.0 aM100 nM [31]
Au-Se NPs NO3- 8.6 mM 16 mM5 mM [32]
Hg2+ 1.0 ppb 143500 ppb
Au-TiO2 NTAs BPA 6.2 nM 0.1 mM38.9 mM [33]
Ag-Si core-shell NPs NAC 2.5 nM 2.5 nM10 mM [36]
NB 1.68 mM 10600 mM [37]
Ag NPs-ssDNA Hg2+ 3 pM 0.01100 nM [38]
Ag NPls Pb2+, Cd2+, 0.5 ng mL 1
0.570 ng mL 1 [39]
Cu2+
Ag NPs E. coli 0.4 pM 0.41.3 pM [35]
Ag NPs-GR AIV H7 1.6 pg/mL 1.6 mg16 ng/mL [40]
Pt NPs H2O2 100 nM 0.0520 mM [43]
Pt/Pt-black H2O2 7 nM 7 nm5 mM [42]
NO2- 12 nM 12 nm5 mM
PtPd-rGO NRs TNT 0.8 ppb 0.013 ppm [44]
b-CD-PtNPs/GNs a-NAP 0.23 nM 0.8220 nM [46]
b-NAP 0.37 nM 3300 nM
Pt/PPy NSs Hg2+ 0.27 nM 5500 nM [45]
rGO-AgPd NPs RAC 1.52 pg mL 1 0.01100 ng mL 1 [48]
SAL 1.44 mL-1 0.01100 ng mL 1
CLB 1.38 mL 1 0.01100 ng mL 1
Pd NCs-PPy NO3 0.45 mM 1001400 mM [49]
Pd NPs-PVP H2O2 8 nM 0.01 mM1 mM [50]
Pd WLNCs/g-C3N4 Ops 0.33 nM 1.0 nM14.9 mM [96]
hupA 1.30 nM 3.9 nM20.8 mM
CNT-PSS/Bi Pb(II) 0.2 nM 2.4434 nM [97]
Cd(II) 0.18 nM 4.4241 nM
SWCNT catechol 2.3 nM 0.12 mM [65]
MWCNTs@GONRs 1-aminopyrene 1.5 nM 8500 nM [98]
GQD-AuNPs Hg(II) 0.02 nM [99]
Cu(II) 0.05 nM
GONRs TNT 4 mM 483 mM [71]
Pd-rGO NO 0.0714 mM [73]
DNA-GO Hg(II) 0.12 nM 0.550 nM [100]
PA/PPy/GO Pb(II) 0.2 nM 24724 nM [74]
Cd(II) 20 nM 4.41339 nM
Macro/meso- carbon nitrobenzene 8 nM 0.240 mM [76]
Macroporous carbon N-acetyl cysteine 0.05 mM 0.118.6 mM [78]
cysteine 0.02 mM 0.1526.24 mM
PANI-NF VOCs 3 ppm 3.0300 ppm [86]
PPy/a-Fe2O3 NO2 5 ppm 5100 ppm [87]
pDA N2H4 1 mM 100 mM10 mM [88]
20 nM
PAMM-Au Catechol 1.74 pg mL 1 50 nM10 mM [84]
PAMAM-SWCNHs-Pt PCT 0.18 mg mL 1 10 pg20 ng mL 1
PAL/ MWCNTs Capsaicin 0.03 nM [92]
Au NPs-BSA-rGO Hg2+ 0.05 nM 0.1130 nM [94]
Fe3O4/Au-AChE OPs 101 cfu mL 1 0.055 nM [95]
SPIMs-WGA E. coli 102107 cfu mL 1 [93]

NPs: nanoparticles; NAC: nitroaromatic compounds; PAA: poly(amic) acid; NB: nitrobenzene; NPls: nanoplates; GR: graphene; AIV H7: avian inuenza virus H7; NRS:
nanoribbons; TNT: trinitrotoluene; b-CD: b-cyclodextrin; GNs: graphene nanosheets; NAP: naphthol; PPy NSs: nanospherical polypyrrole; PPy: polypyrrole; NCs:
nanoclusters; OPs: organophosphorus pesticides; hupA: huperzine; WLNCs/g-C3N4: wormlike nanochains/graphitic carbon nitride; PANI-NF: polyaniline nanobers; VOCs:
volatile organic compounds; PPy: polypyrrole; Pda: polydopamine; PAMAM: poly(amidoamine); PAL: phenylalanine ammonia-lyase; SWCNHs- single-walled carbon
nanohorns; BSA: bovine serum albumin; AChE: acetylcholinesterase; SPIMs: surface of the printed interdigitated microelectrodes; CNT: carbon nanotubes, SWCNTs: single
carbon nanotubes, MWCNTs: multi-walled carbon nanotubes, GONRs: grapheme oxide nanoribbons, GQD: grapheme quantum dots, NPs: nanoparticles,rGO: reduced
graphene oxide, PA: phytic acid.

on bio-nanomaterials for the detection of emerging environmental
pollutants and food safety applications [80,92,93].
Bisetty co-workers have developed an electrochemical biosen-
sor for capsaicin, which extracted from chillifruits, using with a
nanobiocomposite of L-phenylalanine ammonia-lyase enzyme
[92]. In this biosensor platform, the nanocomposite of MWNTs
and phenylalanine ammonia-lyase enzyme immobilized on the Pt
electrode surface was designed. The established biosensor
exhibited a low detection limit of 0.18 mg mL 1. The interaction
of the PAL enzyme with the phenolic component of the capsaicin is
a vital role to enhance the sensitivity of the developed biosensor
platform. Due to the high specicity, controllability, robustness
and ability to function under a wide range of temperatures and
condition, DNA-based biosensor platforms have attained much
interest in the elds of environmental and health care. The
employment of DNA-DNAhybridization, protein-DNA recognition,
etc. based biosensors have been developed for the analysis of
numerous target analytes. For example, recently, Wang et al. have
demonstrated sensitive electrochemical biosensor platform based
on the Au nanoparticles decorated bovine serum albumin and rGO
(Au NPs-BSA-rGO) for the detection of Hg2+ [94]. This resulted
sensor platform exhibited a detection limit of 0.03 nM with a wide
range between 0.1 and 130 nM.
The real-time measurement of acetylcholinesterase (AChE) was
employed by Du co-workers through reactivation from a postex-
posure by considering inter- or intra-individual variation in the
 G. Maduraiveeran, W. Jin / Trends in Environmental Analytical Chemistry 13 (2017) 1023
normal levels of AChE for the detection of organophosphorus
pesticides (OPs) poisons [95]. As shown in Fig. 7, the fabrication of
sensor platform based on coreshell Fe3O4/Au NPs nanocompo-
sites and the process of the electrochemical oxidative desorption
for thiocholine. The measurement of AChE activity from OP-
exposed sample and the parallel measurement of AChE activity are
schematically illustrated in Fig. 7. This OP sensor showed a linear
concentration range of 0.055 nM. To enhance the adsorption
capacity, stability, and retain activity of the bio-nanomaterials,
self-assembled monolayers (SAMs) approach is widely employed
to functionalize the surface of the electrode. For instance, with the
amide bond formation, the reaction can be held between amino
group of protein and reactive succinimidyl group of the 3-
dithiobis-(sulfosuccinimidylpropionate) using the covalent bind-
ing formation on the SAM electrode surface.
On the electrode modication with biomaterials, the short self-
assembling time with mild reaction condition enhances the
performance of the biosensors. Li et al. have developed an
electrochemical impedance immunosensor for the detection of
Escherichia coli O157:H7 based on SAM approach [93]. The signal of
the impedance can be altered by the immobilization of the
biomaterials onto the surface of the printed interdigitated micro-
electrodes (SPIMs). This developed immunosensor showed a low
detection limit of 101 cfu mL 1 and a linear range from 102 to
107 cfu mL 1. This biosensor may use in food safety analysis, which
may lead to a portable biosensor method for routine monitoring of
foodborne pathogens.
7. Conclusions and future outlooks
Development of nanoscale electrode materials for the environ-
mental monitoring and food safety applications has gained
signicant importance, in terms of new functionality, high
sensitivity and specicity as a robust sensor platform. This review
has provided a brief summary of the recent advances in the design
of electrochemical sensor and biosensor platforms, which are
empowered by the unique physicochemical and electrochemical
properties of the nanomaterials, lead to enhance the development
of advanced applications. A list of numerous nanomaterial based
electrochemical sensor and biosensor platforms for environmental
applications discussed in the present review is summarized in
Table 1. The fabrication of the nanomaterial based electrochemical
sensors have been illustrated over the past two decades due to the
ascription of the exceptional intriguing properties, easy surface
functionalization, favourable compatibility, high electrochemical
activity, the great mass and electron transfer property of the
nanomaterials. There is a necessary for the design of advanced
nanomaterials to require to achieve high sensitivity, selectivity and
stability of the sensor and biosensor platforms. The following
related problems to reect in the construction of novel nano-
materials include: (i) size and shape controlled synthesis to
attain the optimal electrochemical active sites, (ii) bi- or tri-
metallic nanomaterials optimization and architectures to
improve the specicity and stability, (iii) discovery of functional
molecule to provide high specicity with analytes, (iv)
correlation between composition, structure, and reactivity of
nanomaterials to design novel nanomaterials with exceptional
selectivity, (vi) discovery of high conductive, chemical and
mechanical stable and great surface area of substrate materials
to improve the electrochemical properties, and (vii) design of the
nanometric interfaces to offer a great platform for the
exceptional electrocatalytic properties, improve the sensitivity
and stability of the sensor platform.
The key factors such as shape, size, architecture, composition,
and functionalization are mainly involved in the enhanced
performance of the electrochemical sensor and biosensor
21
platforms. Owing to the advances in the nanomaterials synthesis,
sensor fabrication, integration and testing analytical measure-
ments, the fast and online-monitoring of emerging environmental
pollutants may offer a possible elucidation towards the recognition
of the highly sensitive sensors. Besides the development of the
sensors with high sensitivity, rapid response and low-cost, the
direct analytical measurements of the developed sensors in the
commercial environmental and food monitoring industries is an
another milestone because of the lack of extensive combined
efforts between multidisciplinary science and engineering dis-
ciplines. This review has delivered a model framework to expedite
the emergence of advances to address the tasks that presently
obstruct the usage of nanomaterials various electrochemical
sensor/biosensor applications, and drawn the requests for future
development. It is expected that the advances of electrochemical
sensor and biosensor platforms based on nanomaterials will be
comprehended to implement of the corresponding directives to
provide a better life for society in the near future with continuous
effort on the advancement.
Acknowledgments
W.J acknowledge the funding support from CAS Pioneer
Hundred Talents Program and National Natural Science Founda-
tion of China under Grant No. 51604253.
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