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Graphite pencil electrodes as electrochemical

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sensors for environmental analysis: a review of

Cite this: RSC Adv., 2016, 6, 91325
features, developments, and applications
Abdel-Nasser Kawde,* Nadeem Baig and Muhammad Sajid

Received 8th July 2016
Accepted 19th September 2016
DOI: 10.1039/c6ra17466c
www.rsc.org/advances
Graphite pencil electrodes (GPEs) are carbon-based electrodes that are recognized by their low cost,
simplicity, commercial availability, ease of modification and disposability. GPEs are attractive substrates
for electrochemical sensing because of their unique feature of “disposability” compared to other
commonly used carbon-based electrodes. Mechanically rigid GPEs are easy to modify and miniaturize.
The sensitivity and selectivity of GPE toward certain analytes can be enhanced by applying different
modification materials. The primary focus of this review article is to highlight the applications of GPEs in
the analysis of inorganic and organic pollutants in different environmental matrices. This review gives
a brief overview of the various types of inorganic and organic pollutants and their impact on the
environment. The key features of modified GPEs that enhance their electrocatalytic activity toward
detection of certain target analytes are critically appraised. In the end, we summarize the current status,
weaknesses and future prospects of GPE based sensors for environmental analysis.

the middle of the 1990s, there were only a few reports on

1. Introduction
The Scopus database reveals that it was probably 1960 when for
the rst time a graphite electrode obtained from an HB pencil
was used as the working anode in polarography without any
modication.1 Though this publication cites another work
published in 1954, where a graphite pencil electrode was used
as a reference electrode, this cited work is difficult to trace. Until
Department of Chemistry, King Fahd University of Petroleum and Minerals, Dhahran
31261, Saudi Arabia. E-mail: akawde@kfupm.edu.sa
modied GPEs for sensing of some analytes2–4 e.g. an antibody
immobilized GPE was utilized as a direct potentiometric
immunoelectrode for detection of atrazine.3 However, these
reports have yet not described any disposable and renewable
GPEs. During the same period, some disposable electrodes such
as metal electrodes or carbon materials deposited metal
substrates were being used but their disposability was only good
from an economic perspective and the issue of occupational
and environmental safety was another aspect to be considered

Abdel-Nasser Kawde received his Nadeem Baig received his B.S

B.S. (1991) and MS (1996) in
chemistry from Assiut Univer-
sity, Egypt. He received his Ph.D.
(2003) in analytical chemistry
from New Mexico State Univer-
sity, New Mexico, USA under the
supervision of Professor Joseph
Wang. He has co-authored
more than 100 journal and
conference publications, and 15
US patents. His current research
focuses on the development and
characterization of electrochemical-based sensors and biosensors
utilizing macro-, micro- and nanomaterials for various applica-
tions.
(Hons.) 2008 from University of
the Punjab and M. Phil. from
University of Engineering and
Technology, Lahore in 2012.
Aer that, he joined the doctoral
program at King Fahd University
of Petroleum and Minerals,
Saudi Arabia on Jan. 2013. Mr
Baig is working on the develop-
ment of electrochemical sensors
for various applications in the
biological and environmental
issues under the supervision of Professor A. Kawde. He is also
interested in drug study. He has published ve articles in ISI-
indexed journals and has one patent.

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RSC Advances
because of their applications in trace level detection of toxic
substances.
To the best of our knowledge, renewable GPE was for the rst
time reported in 1997 for stripping voltammetry of cadmium
and lead.5 Although for writing purposes, the renewable
graphite pencils were introduced many years ago, but their
potential as low-cost, readily available, and the renewable
electrode was not realized up till 1997. Some notable works that
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were conducted in following years include detection of RNA and
DNA,6 labels free detection of DNA hybridization,7,8 and analysis
of trace metals.9
The feature of renewable writing pencils where lead can be
extruded to any desired length from the holder is very well
utilized in GPEs. Aer each electrochemical measurement, the
used surface of GPE can be easily renewed by removing the
extruded part. Moreover, the sensing area of the pencil exposed
in the solution can be easily controlled according to the
requirement of analysis. From the green chemistry perspective,
the only small material is used as an electrode and can be
readily disposed of aer use.
GPE is a subtype of the graphitic electrodes that has
specialized characteristics of the high surface area, good
conductivity and ease to use. However, the uniqueness of GPE is
credited to some of its specic properties like it is cheap,10
commercially available and easily disposable. Moreover, GPEs
are mechanically rigid, easy to modify and miniaturize.11 GPEs
are most attractive electrodes because they offer a simple and
faster surface renewal compared to other commonly used
electrodes which involve tedious surface polishing procedures.
Because of renewable surfaces, GPEs are expected to give
reasonably reproducible results. Additionally, GPEs show
strong adsorption properties, low background current, and
wide potential window.12
As a result of industrial revolution and urbanization, human
environment is badly affected by the variety of inorganic and
organic pollutants. These pollutants have been identied as
a serious challenge for the survival of human and wildlife.
Hence, some of these pollutants have been regulated by
Muhammad Sajid received his
Ph.D. degree in Chemistry in May
2016 from King Fahd University
of Petroleum and Minerals, Saudi
Arabia. During his Ph.D., he
worked on analytical methods
development for trace level
determination of endocrine dis-
rupting compounds in biological
samples. His research interests
are focused on the development
of miniaturized techniques for
extraction of emerging pollutants
in environmental, food and biological samples prior to their
instrumental analysis. He is also interested in studying the impact
of emerging pollutants on humans and the environment. He has co-
authored more than 10 articles in ISI-indexed journals.
91326 | RSC Adv., 2016, 6, 91325–91340
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Review
national and international environment protection agencies
and their allowable limits have been dened. No doubt, last few
decades have witnessed great progress in the instrumentation
for analysis of a variety of inorganic and organic pollutants but
the high cost of these sophisticated instruments itself a big
challenge in low resource setups. In addition to cost, these
instruments are not suitable for in eld applications. Simple,
low-cost, efficient, portable and commercially available instru-
ments or electrochemical sensors are desired to fulll the
demand of worldwide monitoring of pollutants in different
matrices.13 Because of their simplicity, low-cost, large-scale
availability, GPE based electrochemical sensors can be a good
choice for environmental analysis in limited resource setups.
In the recent years, there has been observed an increasing
trend for the applications of GPE based electrodes in the envi-
ronmental analysis. To the best of our knowledge, this is the
rst review article that covers environmental analytical appli-
cations of GPE. Hence, this review gives brief description of
(i) Highly toxic pollutants from inorganic and organic origin.
(ii) Applications of GPE based electrochemical sensors for
detection of these pollutants in environmental matrices.
(ii) Properties of the GPE and modied GPEs which enhance
the sensitivity and selectivity of the electrode toward particular
target species.
Fig. 1 gives a pictorial description of the features of GPE that
have been covered in this review article.
2. Electrochemical analysis of
inorganic pollutants at GPE
The presence of metals, metalloids and other inorganic
pollutants in environmental matrices is the most important
environmental problem of the modern age. Both natural and
anthropogenic sources contribute signicant amounts of inor-
ganic pollutants in the environment. In the coming sections, we
enlist and highlight the importance of studying inorganic
pollutants in the environment. The applications and potential
of GPE based sensors for detection of inorganic pollutants are
critically discussed in each section.
2.1. Metallic pollutants
Heavy metal pollution is a global environmental challenge.
Heavy metals are distributed in the environment as a result of
their increased applications in domestic, industrial and agri-
cultural processes. The heavy metals such as mercury, lead,
cadmium, chromium and arsenic are considered priority
pollutants and have been regulated by a number of national and
international environmental agencies. Metallic pollutants are
recognized as “systematic pollutants” and they cause various
ailments in the human body including damage to different
organs. Some metals have been classied as carcinogens (well
known or suspected) by USEPA.14 Metal toxicity to an individual
depends on upon many factors such as kind of exposure
(environmental or occupational), dose and period of exposure
and nature of the metal itself. However, it is obvious that
continuous exposure to low-level concentrations of these
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Fig. 1 Features, modification materials and applications of graphite pencil electrode.
pollutants may lead to serious health implications. From the
polluted environment, these metals may enter to food chain
and thus to the bodies of humans, other animals, and aquatic
organisms. Therefore, sensitive analytical methods are needed
to measure the levels of heavy metals in the environment. In
order to deal with a global environmental challenge posed by
heavy metal pollution, simple, efficient, portable and cost-
effective analytical methods are always desired. The last few
decades have witnessed some major advancements in analytical
instrumentation for analysis of heavy metals. The instruments
like atomic absorption spectroscopy (AAS) and inductively
coupled plasma-mass spectrometry (ICP-MS) have been widely
used for determination of metals in different matrices.
Although, these instruments are highly sensitive and selective,
but some major issues are associated with them. They are very
expensive, require a number of consumables, and their porta-
bility for in eld applications is a big challenge. Before the
analysis, extended procedures of sample preparation are
needed. Moreover, analysis is destructive, time-consuming and
expert operators are required. Electrochemical methods for
detection of heavy metals are simple, efficient, cost-effective,
non-destructive and do not require extended sample prepara-
tion procedures for common environmental matrices such as
water and soil. Electrochemical methods can provide adequate
sensitivity and selectivity for detection of metals. In addition,
these methods can be used for speciation and multi-elemental
analysis. GPE based electrodes are very cheap and easily avail-
able and can be used to perform cost-effective analysis in
limited resources setups. Hence, in the following paragraphs,
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we described some applications of GPE and modied-GPE for
sensing of metals in environmental samples. Table 1 lists
applications of GPE based electrodes for detection of inorganic
analytes in different environmental matrices.
2.1.1. Cadmium. Different anthropogenic activities result
in accumulation of cadmium in soil. This cadmium is then
transferred to the human body through consumption of
contaminated plants and food. The other sources may include
smoking and occupational exposure. The fever and muscle ache
that leads to respiratory problems and damage to kidneys.
Exposure to cadmium has also been linked with lung and
prostate cancer. So its environmental monitoring with simple,
cheap and efficient methods is desired.
An ISE was fabricated by electropolymerization of 4-vinyl
pyridine on 2B pencil graphite as ionosphere for Cd2+. The
electrode gave good limit of detection (LOD) down to 2.5
108
M and relatively a broad pH range 4.0–7.5 for cadmium
measurement. The major advantages of this modication are
cheap material, easy modication and potential to apply in in
situ measurements of cadmium in real samples. The developed
electrode was used to determine Cd2+ by using the potentio-
metric method in different environmental (soil), food (tea,
vegetables) and biological (cow liver, kidney, heart and chicken
liver and heart) samples.15
2.1.2. Lead. Lead is so, malleable, resistant to corrosion,
ductile and has low melting points. Due to these features, it has
been widely used in automobile, ceramics, plastic and paint
industries. Lead poisoning is a serious issue, and accumulation
of lead in the body may prove fatal in certain conditions. As
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Table 1 Applications of GPE based sensors for detection of various inorganic pollutants in environmental samples

Detection in
Electrode Analyte Matrix Medium/pH Technique Linear range LOD real samples Ref.

PSS/CnP/GPE Cu(II) Mineral, sea and 0.1 M KCl/3.0 DPASV — 0.11 mg L1 Yes 21
river water
Cu-P4R/PPy/GPE Cu(II) Tap water pH range 4.0–6.0 Potentiometry 1
105 M to 6.7
106 M Yes 22
5
102 M
Cu–Car/PA/GPE Cu(II) Green tea leaves, 6.0 Potentiometry 5
106 to 2
106 M Yes 23
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black currants, 1
101 M

sour cherry juice
P4VP/GPE Cd(II) Soil, tea, cabbage, 6.4 Potentiometry 1
107 to 2.51
108 M Yes 15
liver, kidney, heart 1
101 M
Bi-NPs/ Pb(II) — 0.1 M NaOAc/4.5 DPV 0.4–10.8 mmol L1 1.7 nmol L1 No 17
puMWCNT/GPE
DPC/PANI/GPE Cr(VI) Tap water 2.0 Potentiometry 1
106 to 8
107 M Yes 18
1
101 M
Tar/PPy/GPE Zn(II) Barley akes, 5.0 Potentiometry 1.0
105 to 8.0
106 M Yes 19
rice, dry milk 1.0
101 M
NG/PG/BiE Pb(II), Tap water 0.1 M acetate SWASV 2–20 mg L1, 0.17 & 0.22 mg L1, Yes 20
Cd(II), buffer/4.6 10–100 mg L1 0.09 & 0.09 mg L1,
Zn(II) 0.13 & 0.20 mg L1
Ag/FeOOH/GPE H2O2 Disinfectant 0.1 M PBS/7.2 Amperometry 0.03–15.00 mM 22.8 mM Yes 32
PtNPs/GPE H2O2 — 0.1 M PB/7.0 Amperometry 10–110 mM 3.6 mM No 30
PdNPs/GPE H2O2 — 0.1 M PB/7.0 Amperometry 10–140 mM 0.045 mM No 31
PVF+/MWCNTs/ NO2 Mineral water 0.05 M PB/7.4 DPV 1–400 mM 0.1 mM Yes 33
GPE
Poly(PyY)/GPE NO2 Salami 0.1 M PBS/4.0 Amperometry 1–100 mM 0.5 mM Yes 34
Au NPs/GPE N2H4 Drinking water 0.1 M PB/5.0 SWV/ 0.05–1000 mmol L1, 42 nmol L1, Yes 12
amperometry 25–1000 mmol L1 3.07 mmol L1

a result of oxidative stress, lead poisoning can lead to disorders
in central nervous system, renal and reproductive system.16
Recently, GPE was modied by the subsequent application of
puried MWCNTS and bismuth NPs. The modied electrode
was termed as Bi-NPs/puMWCNTS/GPE and was used for
analytical measurement of Pb2+ ions. The electrode showed
excellent electrocatalytic activity due to enhanced surface area
of the modied surface and proper LODs down to 1.7 nM were
obtained by using differential pulse voltammetry. As the major
focus of this work was a synthesis of bismuth nanostructures,
modied electrode was not used to demonstrate its feasibility
for real environmental samples.17
2.1.3. Chromium. Chromium is also widely used in a range
of industrial applications including leather tanning,
manufacturing of alloys, electroplating, wood treatment and
metal smelting. In the environment, chromium exists in two
oxidation states, Cr(iii) and Cr(VI). Cr(VI) is considered toxic
anion because of its high mobility and water solubility
compared to Cr(iii). Cr(VI) is also reported to have carcinogenic
effects. Hence, instead of measuring total chromium content in
the environment, it would be more suitable to measure only
hexavalent chromium. Electrochemical methods are thus
capable of speciation analysis because of different redox
potential values for various oxidation states of the same
element. In order to detect Cr(VI) by potentiometric method,
GPE was electrochemically modied with polyaniline in pres-
ence diphenyl carbazide and resulting modied GPE was
termed as GPE/PANI/DPC. The resulting electrode gave a good
linear range from 106 to 101 M with a limit of detection 8.0

107 M at pH ¼ 2. The electrode showed good tolerance against
interfering ions and no signicant decrease was observed in the
response for the period of one month, showing a good shelf
life.18
2.1.4. Zinc. Zinc and different compounds derived from it
are extensively used in industrial processes such as alloy
formation, wood treatment, electroplating, rubber processing,
dye, pharmaceutical products, and paints. In medical, zinc is
used in mouthwashes, disinfectants, antiseptics and mineral–
vitamin formations because of its biocidal activity. It is
a micronutrient whose small quantiles are essential to the
human body, but its high concentrations can cause different
ailments including vomiting, fever, pulmonary problems,
nausea, and renal disorders. Therefore, highly efficient, cheap
and simple methods are needed to monitor the zinc contents in
the environmental and biological samples. A potentiometric
ion-selective electrode for zinc was fabricated by modication of
GPE with polypyrrole nano-lm. Polypyrrole was electrochemi-
cally deposited on GPE in the presence of tartrazine as a dopant.
This electrode showed analytical features such as wide linear
range, high selectivity and good stability and reasonably low
limit of detection of 8.0 mM at optimum pH. Applications of the
modied electrodes were extended for testing of Zn2+ in barley
akes, rice and dry milk.19
There are only few reports which describe simultaneous
detection of more than one metal ions on modied GPEs. The
Naon graphene nanocomposite pencil graphite bismuth lm

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electrode (NG-PG-BiE) was used for simultaneous detection of
Pb2+, Cd2+ and Zn2+ ions in tap water using square wave anodic
stripping voltammetry. The NG-PG-BiE exhibited detection
limits of 0.17, 0.09 and 0.13 mg L1 for Zn2+, Cd2+ and Pb2+ much
lower than below the USEPA allowable limits of 5 mg L1, 5 mg
L1 and 15 mg L1 for Zn2+, Cd2+ and Pb2+ respectively.20
2.1.5. Copper. Copper is essential metal that is present in
all organisms, and its excess or deciency is associated with
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different diseases. Copper is released into the environment as
a result of mining and industrial process. Human is exposed to
copper through the environment and contaminated food.
Hence, accurate monitoring of copper in the environment is
desired. Polystyrene sulfonate–carbon nanopowders composite
was used to modify GPE for determination of Cu2+ in mineral,
river and seawater using differential pulse anodic stripping
voltammetry. This simple to fabricate sensor showed good
sensitivity toward Cu2+ and tolerance against interfering cations
and anions. This method showed LOQ of 0.37 mg L1 and it was
much lower than the allowable limit of copper in waters regu-
lated by European (2 mg L1) and Spanish (1 mg L1) Drinking
Water Directives.21
Ion-selective electrodes have shown some exciting applica-
tions in the current years because of their ability to analyze the
target ions rapidly in small sample specimen with high accuracy
and reproducibility. Potentiometric based ion selective elec-
trodes are convenient because of their low cost, non-destructive
analysis, and not affected by turbid or colored samples. Poly-
pyrrole conducting polymer doped with Ponceau 4R azo dye
based modied GPE was used for selective potentiometric
determination of Cu2+ in water. The pyrrole monomer was
electrochemically polymerized on GPE in the presence of Pon-
ceau 4R azo dye as a dopant. The presence of the dopant in
electropolymerization generates selective recognition sites in
the formed polymer, and these sites can interact selectively with
Cu2+ ions. This modied electrode showed good LOD values
down to 6.7 mM. LODs remained unchanged for the shelf life of
21 days, and a slight change was observed aer 60 days. The one
limitation for this electrode is that it is only suitable in acidic
medium (pH, 5).22 Another similar work is reported where GPE
modied with conducting polyaniline doped with copper car-
moisine dye complex was used for potentiometric monitoring of
Cu2+ in green tea leaves, black currants, and sour cherry juice.
This modied electrode showed a very fast response (20 s) and
good limit of detection 2.0 mM.23
2.2. Comparison of GPE based sensors and other
instrumental methods for analysis of metals
Here it will be suitable to compare the GPE based electro-
chemical methods and other instrumental methods which are
used for detection of metallic impurities in environmental
samples. Flame atomic absorption spectrometry (FAAS) is one
of the major technique used for determination of metals such
as cadmium, lead, zinc and copper in different matrices. The
disadvantages that are associated with FAAS are mainly related
to matrix interference on the analyte signal and higher limit of
detections than the normal concentration of metals present in
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real samples. Thus, removal of interferences and improvement
in LOD is achieved through separation and preconcentration of
the metals prior to analysis.24 This kind of sample preparation
itself is a tedious job because multistep processes are involved
that may comprise reaction (derivatization), extraction, sepa-
ration, preconcentration and determination. Moreover, the
accuracy and reliability of sample preparation assisted FAAS
depends upon the number of steps involved. It is matter of fact
that these sample pretreatment methods have made trace
element assays more convenient, but more oen they require
large sample or reagent volumes (several tens to hundreds of
milliliters) to get high enrichment factors or preconcentration
factors. However, when it is difficult to obtain such large sample
volumes, these techniques led to low enrichment factors and
high detection limits.25 When dealing with trace elements, total
content analysis as well as speciation analysis both are very
important. Trace metals exist in different oxidation states and
some metal species have been reported to show varying toxic-
ities in their different oxidation states, for example, hexavalent
chromium is much more toxic than trivalent chromium.26 In
order to nd out the role of trace element species in different
diseases, recent research in area of trace element analysis is
shiing from total content to speciation analysis. Hence, very
efficient extraction methods that would be capable of selective
speciation and then highly selective detectors are desired in
analytical instruments.27
In general, no specialized sample preparation is necessary
for electrochemical methods. In addition to that electro-
chemical methods are cost and time effective. For the trace
elemental analysis, the speciation can be easily performed by
simply altering the detection potential. Moreover, very low
LODs can be achieved by electrochemical methods without
performing any sample preconcentration. When particularly
talking about graphite pencil electrodes, they are easily avail-
able in the market and cost much lesser than other carbon or
metal-based electrodes. However, the automation of GPE based
electrochemical methods presents a challenge that need to be
addressed for successful commercialization of such analytical
tools. Table 2 compares GPE based sensors with other instru-
mental methods.
2.3. Other inorganic pollutants
In addition to the metals, other substances such as hydrazine,
hydrogen peroxide, suldes, cyanide, perchlorate, oxides of
nitrogen and sulfur have a great environmental impact as
inorganic pollutants. Few of these have been electrochemically
detected in different environmental matrices using GP based
electrodes. A brief account of these pollutants is provided in
coming sections.
2.3.1. Hydrazine (N2H4). Hydrazine is an inorganic mole-
cule with molecular weight 38 g mol1. Hydrazine is used in
many industrial applications such as pesticide in agriculture,
starting material for many chemicals and plastics, intermediate
in pharmaceutical and corrosion control agent in the treatment
of water boilers. As it is lightweight, volatile and water-soluble
colorless liquid, it has the ability to be absorbed by oral,
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Table 2 Comparison of GPE based electrochemical methods with other instrumental methods

Metal Matrix Sample preparation Detection method Detection technique LOD Ref.

Cadmium Water Pyrolysis vapor generation Spectroscopic AFS 2.2 ng mL1 77

Water and food Modied MNPs based SPE Spectroscopic FAAS 3.71 ng mL1 78
Water and food Nanomagnetic task specic Spectroscopic FAAS 0.5 ng mL1 24
ionic liquid as a selective
sorbent in SPE
Water and food Pyridine-functionalized Spectroscopic FAAS 0.04 ng mL1 79
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magnetic nanoporous
silica material
Soil, tea, cabbage, — P4VP/GPE based Potentiometry 2.51
108 M 15
liver, kidney, heart electrochemical
Lead Water and human air Magnetic ion-imprinted Spectroscopic GFAAS 2.4 ng L1 80
polymer (MIIP) nanoparticles
Water samples Air-assisted liquid–liquid Spectroscopic FAAS 1.36 ng mL1 81
extraction
— — Bi-NPs/puMWCNT/GPE DPV 1.7 nmol L1 17
based electrochemical
Copper Water, food and Switchable solvent-based Spectroscopic FAAS 1.8 ng mL1 82
hair samples liquid phase microextraction
Water samples Temperature-assisted Spectroscopic GFAAS 1.82 ng L1 83
dispersive liquid–liquid
microextraction
Mineral, sea and — PSS/CnP/GPE based DPASV 0.11 mg L1 21
river water electrochemical
Tap water — Cu-P4R/PPy/GPE based Potentiometry 6.7
106 M 22
electrochemical
Green tea leaves, — Cu–Car/PA/GPE based Potentiometry 2
106 M 23
black currants, electrochemical
sour cherry juice
Zinc Water samples Temperature-assisted Spectroscopic GFAAS 0.89 ng L1 83
dispersive liquid–liquid
microextraction
Water samples Solid phase extraction Spectroscopic FAAS 0.24 ng mL1 84
Water samples Surfactant-based dispersive Spectroscopic FAAS 85
liquid–liquid microextraction
Barley akes, — Tar/PPy/GPE based Potentiometry 8.0
106 M 19
rice, dry milk electrochemical

dermal and inhalation pathways in the living organisms.
Hydrazine has been identied as a highly toxic substance to the
living organisms because its exposure may lead to serious
damage to kidney, liver, lungs and central nervous systems. It
also affects negatively the reproduction system and its carci-
nogenic effects have also been reported. Hence, simple, low cost
and reliable analytical methods are desired to monitor the
environmental levels of hydrazine. Recently, AuNPs modied
GPE was prepared by immersing the GPE in a test tube con-
taining a solution of ascorbic acid and gold(III) chloride and
heating it up to 75  C for 15 minutes in water bath. This
modication procedure does not require any cross-linking
molecules and describes direct attachment of AuNPs on GPE.
This modied electrode was used for detection of N2H4 in
drinking water, and excellent limit of quantication down to
100 nM and limit of detection 42 nM was achieved using square-
wave voltammetry as a mode of detection.12
Later on, Chelladurai Karuppiaha et al. have reported highly
sensitive sensor Au NPs/AG/SPCE for detection of hydrazine.
This sensor was more sensitive compared to simple Au NPs/
GPE. The sensitivity of the SPCE was enhanced by coating the
dispersed graphite and dried cast graphite was later on elec-
trochemically activated. On AG/SPCE the Au NPs were electro-
chemically deposited and this activation process of graphite
and the presence of Au NPs on the surface of SPCE made the
sensor highly sensitive towards hydrazine and very low LOD
down to 0.57 nM achieved.28 However, in case of Au NPs/GPE no
activation of graphite was involved prior to modication with
Au NPs.
2.3.2. Hydrogen peroxide (H2O2). H2O2 has widespread
applications in enzymatic reactions, food industry, organic
products, disinfectants, bleaches, hair dyes and various other
industrial, environmental and biomedical processes. It is also
naturally present in some foods. It has been reported to have
reasonable toxicity against living organisms.29 Because of its
increasing use in different applications; it is critical to monitor
H2O2. For sensing of H2O2, compared to spectroscopic
methods, electroanalytical methods are more attractive because
of their fast response and high sensitivity.30 Although conven-
tional methods of H2O2 are based on enzyme based sensors but
due to high cost of enzymes and complex synthetic procedures

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for modication, non-enzymatic electrochemical sensors are
getting more popular.
Some sensitive analytical methods based on a modication
of GPE have been developed for detection of H2O2. NPs and
nanomaterials modied GPE showed good electrocatalytic
activity toward H2O2 detection. Platinum NPs modied GPE was
fabricated for highly sensitive detection of H2O2. This modi-
cation was achieved by a very simple process which involves
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dipping of GPE in an aqueous solution of 0.5 mM (NH4)2PtCl4
and 0.55 mM ascorbic acid followed by heating at 75  C for 15
min. The electrode gave excellent tolerance against interferes
and LOD of 3.6 mM was achieved.30 In another work, palladium
NPs modied GPE was used for sensing of H2O2. This method
also involves the facile synthesis of Pd NPs on the surface of
GPE. In this Pd NPs were prepared by the very simple approach
by adding aqueous solution of ascorbic acid (AA) to aqueous
solution of (NH4)2PdCl4 and stirring it for 15 min at room
temperature. The color change of (NH4)2PdCl4 from pale yellow
to dark brown was indicative of NPs formation. GPE was then
incubated in a solution of NPs for 15 min at room temperature.
The H2O2 was determined in the aqueous medium using the
amperometric technique. The modied electrode was capable
of detecting H2O2 at nanomolar levels by amperometric
method, and LOD of 45 nM was obtained which was much lower
than the LOD obtained at bare GPE under the same set of
experimental conditions (0.58 mM).31
In another work, Ag/FeOOH nanocomposites were immobi-
lized on GPE for amperometric detection of H2O2. The rationale
behind employing FeOOH nanomaterials was their high surface
area which can provide better support for AgNPs immobiliza-
tion. The developed electrode showed good long-term stability
and was able to retain 90% of the signal aer 3 weeks of
modications. LOD of 22.8 mM was achieved and method was
used to measure H2O2 in disinfectants.32
2.3.3. Nitrite ion (NO2). Nitrite ion is an intermediate in
the nitrogen cycle. It results from oxidation of ammonia or
reduction of nitrate. It is used as a food preservative in the food
industry. It is hazardous because it combines with blood
pigments to produce meta-hemoglobin, which in turn, depletes
oxygen in tissues. It forms carcinogenic N-nitrosamines upon
reaction with secondary amines. A polymer nanocomposite
modied GPE was formed by single step electropolymerization
of poly(vinyl ferrocene) (PVF) in the presence of MWCNTs. The
resulting modied electrode was termed as poly(vinyl ferroce-
nium) (PVF+)/MWCNTS/GPE. The electrochemical detection of
nitrite was carried out in commercial mineral water using DPV,
and a LOD of 0.1 mM was achieved.33 Similarly, in another work,
pyronin y modied GPE was utilized for amperometric detec-
tion of nitrite and LOD of 0.5 mM was achieved.34
3. Electrochemical analysis of organic
pollutants at GPE
The rapid industrialization in the modern era resulted in the
release of the toxic organic pollutants into the environment.
Although most of the industries try to detoxify or degrade these
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organic pollutants by physical, chemical or biological means
but still signicant amounts of these pollutants are released
into the environment. Organic pollutants are famous by
different names including “emerging organic pollutants”,
“priority pollutants”, “endocrine disrupting compounds” etc.35
A continuous monitoring of these hazardous chemicals is
necessary to take precautionary measures for sustainability of
the healthy environment. In the coming section, we discuss the
applications of GPE based sensors for detection of different
classes of organic pollutants in environmental matrices.
3.1. Phenolic compounds
Phenolic compounds are very common and abundant envi-
ronmental pollutants. Most of the phenolic compounds induce
very severe health problems, and they have been classied as
hazardous wastes and virulent pollutants by the United State
Environmental Protection Agency.36 They adversely affect
human health by accelerating weight loss and weariness.
Phenols are reported to cause respiratory cancer, cardiac and
immune system disorders in case of severe exposures. The
applications of GP based electrodes for high-sensitivity detec-
tions of different phenols are given in following sections.
3.1.1. Phenol. Recently, a very simple method for the
determination of phenol was developed. In this method, GPE
surface was charged by pretreating in NaOH solution. The
charged GPE showed the capability of self-electropolymerization
of phenol on its surface, and this led to the sensitive detection of
phenol. The self-electropolymerized phenol was detected using
square wave voltammetry. Very low limit of detection (4.17 nM)
was achieved using this pre-charged sensor.37
3.1.2. Nitrophenols. The simplest phenol derivative, 4-
nitophenol, is a major threat to the environment. 4-Nitrophenol
is widely used in the fungicides, pesticides, and organic dyes
and also in some pharmaceutical products. Eventually, as
a result of excessive use of these products, the 4-nitrophenol is
released into the environment. It has good solubility in water,38
and it does not degrade easily into other components, which in
turn make it more persistent in the ground water. In addition, it
is considered as carcinogenic and poses a serious threat to the
human health.39 A-N Kawde, and M. Aziz introduced a single
step modication of GPE by electrochemical reduction of the
Cu(II) on its surface. The Cu is more cost effective compared to
Au, Ag, and Pt. The amperometric based electrochemical
method was developed for the determination of 4-nitophenol
and the wide linear range was obtained from 50 to 850 mM with
LOD of 1.91 mM. The presence of potential interferences like
phenol, 4-amino phenol and 3,4-dichlorophenol showed no
effect on the detection of 4-nitopheneol.40 In another method,
the pencil graphite electrode was modied by the bismuth lm
and was used for the simultaneous analysis of 2-nitrophenol
and 4-nitrophenol. Differential pulse voltammetry was used for
the electrochemical analysis of 2-nitrophenol and 4-nitro-
phenol. Bismuth lm electrodes are considered as alternate of
the mercury lm electrode due to environmental friendliness.41
3.1.3. Alkylphenols. Alkylphenols added into the environ-
ment due to the degradation of alkyl phenol polyethoxylates
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which is used in the detergent formation, fuel additive, re
retardant, antioxidant, thermoplastic elastomers, and phenolic
resins. I. David et al. compared the response of the CNT/GPE
and PGPE electrode for 4-tert-octylphenol. The CNT on GPE
surface instead of increasing the current, the current was
decreased while pretreatment signicantly enhanced the
current. The PGPE was used for the determination of 4-non-
ylphenol, 4-octylphenol and 4-tert-octylphenol by applying
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differential pulse voltammetry and developed method gave low
detection limits 0.42, 0.25, and 0.77 mM.11
3.1.4. Bisphenol A. Bisphenol A (BPA) belongs to the family
of endocrine disruptors. Endocrine disrupters are the chemicals
which interfere with normal hormonal activity in the human
and wildlife. BPA is used as intermediate in the manufacturing
of automotive lenses, building materials, thermal paper,
compact disks, protective window glazing, adhesive, paper and
protective coatings. It is also used in the processing of PVC
plastics. The water solubility of the bisphenol A is 120–300 mg
L1. The high solubility of the BPA in water is something which
raises concerns about its toxicity to aquatic and human life.42
The striking effect of the BPA is on fetal and early childhood
development. It also has an adverse effect on sexual differenti-
ation and the brain development. It also reduces the sperm
quality, enhances the risk of cancers and affects the thyroid
hormone functions. The high level of BPA is observed in the
condition of obesity, diabetes, and liver dysfunction. It is really
dangerous for the fetus, pregnant women, and children.43 It is
highly important to nd out the BPA concentrations in the
water using efficient and cost-effective analytical strategies. The
GPE was modied with polyaniline (PANI) and multiwalled
carbon nanotubes (MWCNTs) for detection of BPA. PANI is
extensively used conductive polymer for the electrochemical
sensor fabrication due to its high electrocatalytic activity and
the biocompatibility. On the other hand, the MWCNTs have
great attraction for the sensing applications of the organic
compounds due to high conductance, good adsorptive capa-
bility and high specic surface area. By using amperometric
technique this modied GPE has shown wide linear range of 1–
400 mM with LOD of 10 nM for BPA. Moreover, PANI/MWCNTs/
GPE was applied to detect BPA in water extracted from baby
bottles.44 In another work, A. Ozcan used the synergistic effects
of sodium hydroxide and the lithium perchlorate for the
pretreatment of the GPE. The electrochemical pretreatment
could enhance the selectivity and the sensitivity of the relevant
analyte. In this case, pretreatment electrolyte improved the GPE
surface signicantly for the electrooxidation of BPA. The
adsorptive stripping differential pulse voltammetry was used for
the determination of BPA. The limit of detection was improved
to 3.1 nM compared to above mentioned PANI/MWCNTs/GPE.
This PTGPE was applied to determine BPA in tap and river
water.45
3.2. Organic dyes
A lot of dyes are released into the water as a residue during the
coloring process in the textile industry and severely pollutes the
environment. In dying process, almost 10 to 15% and in some
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Review
conditions, up to 50% dyes are wasted and released to the
aquatic bodies. Azo dyes are the commonly used dyes and
contain azo group (–N]N–). The presence of azo dyes in the
water has adverse effect on the aquatic life and the human
health.46
3.2.1. Chrysoidine. One of the azo dye is chrysoidine that
has brownish red color. Chrysoidine is used in the dying of
leather, plastic, natural and synthetic ber, cosmetics, food-
stuff, waxes, and papers. In the case of inhalation, dermal
exposure, and oral ingestion, it induces acute and chronic
toxicity. Hence its use in foodstuff has been banned. Moreover,
it is also considered as carcinogenic. In some countries, it is
being used to disinfect the sh skin. Hence, monitoring of its
environmental concentrations is highly important from health
and safety perspective. A. Ensaa et al., studied the interaction
of ds DNA with the chrysoidine to develop a sensitive method
for its detection in the aquatic system. It has been observed that
DNA/MWCNTs-PDDA/GPE surface can adsorb chrysoidine more
efficiently and strongly compared to the bare GPE surface. As
the guanine and adenine are electrochemically active nucleo-
tides their electrooxidation current reduced due to the adsorp-
tion of the chrysoidine, and this is another tool for the
measurement of the analyte. A good linear range was obtained
for DNA/MWCNTs-PDDA/GPE sensor ranging from 0.05 to 15.0
mg mL1 with LOD of 0.03 mg mL1 by using DPV. The developed
method was applied on textile effluents, sauce, and the sh
samples.47
3.2.2. Sulfanilamide. Sulfanilamide is used in the synthesis
of azo dye. Sulfanilamide is the rst chemically synthesized
antimicrobial agent, and it is also utilized in some drugs for the
treatment of throat, urinary tract, and vaginal infections.
Sulfanilamide is also found in the animal products and at high
concentrations, it has been reported to induce allergic effects.
Moreover, it is also toxic to the aquatic animals. Molecularly
imprinted polymer (MIP) based electrochemical methods are
highly selective and sensitive for the determination of the
relevant analyte. In molecularly imprinted polymer based elec-
trochemical methods, the complementary cavities are formed
for the analyte, which makes it highly selective towards the
target analyte. These cavities are formed by initiating the poly-
merization in the presence of the analyte and aerward the
analyte is extracted out. Molecular imprinted polymer based
graphite pencil electrode was prepared from the electro-
polymerization of the pyrrole for determination of sulfanil-
amide (Fig. 2 describes schematic of MIP modied GPE). DPV
was used for the sensing of sulfanilamide. It resulted in two
linear ranges 5.0
108 to 1.1
106 M and 1.1
106 to 48

106 M. The MIP/PPy/GPE applied to the ground water for
detecting sulfanilamide and the fabricated sensor was highly
sensitive with LOD of 2.0
108 M.48
3.2.3. Sudan dyes. In chemical industries, the Sudan dyes
are used as the coloring agent for waxes, fats, oils, shoes, petrol,
spirit varnishing, petrol and printing inks. Sudan dyes are
considered as carcinogenic by the International Agency for
Research on Cancer (WHO). Due to carcinogenic nature of the
Sudan dye, its use as a coloring agent in the food products is not
allowed by national and international food regulations. The
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Fig. 2 Schematic representation of electrochemical detection of SN using molecularly imprinted PPy films on GPE. Reproduced from
permission. Copyright 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
method development for the detection of Sudan dyes is very
important due to its toxicity. A sensitive method has been
developed for Sudan II dye. Interaction of dsDNA and the Sudan
II was investigated on the pencil graphite electrode surface. The
electrical response of the guanine and the adenine decreased in
the presence of Sudan II, and this interaction was further
conrmed by absorption spectrophotometry. The decrease in
current may be due to the shielding of the oxidizable group of
the guanine and the adenine by Sudan II. The linear range ob-
tained by the interaction of dsDNA and Sudan II was 0.5–6.0 mg
mL1 with LOD of 0.4 mg mL1. The direct determination of
Sudan II was done by adsorptive stripping differential pulse
voltammetry on the pretreated pencil graphite electrode. The
pretreatment efficiently activated the surface for the analyte,
and linear range obtained 0.0015–0.30 mg mL1 with a very low
limit of detection 0.00007 mg mL1. The interferences have very
small effect on the determination of Sudan II. Moreover, the
satisfactory recoveries of the dye were obtained from the chili
and ketchup sauce.49
3.3. Pesticides
The pesticides represent a broad class of chemicals which is
further divided into insecticides, herbicides, fungicides,
nematicides, molluscicides, and rodenticides. No doubt, pesti-
cides have played a major role in increasing food production
worldwide but at the same time, their excessive use has led to
serious health threats to the human and wildlife. The excessive
use of pesticides results in their accumulation in food, soil, and
water. It is reported that almost one million people die or suffer
per year from chronic diseases resulted from exposure to
pesticides.50 Chlorpyrifos is the commonly used organophos-
phate pesticide, and its exposure can initiate disorders in
neurological and the autoimmune system. A method has been
developed for the trace level determination of the chlorpyrifos
by fabrication the molecular imprinted polymer modied
pencil graphite electrode. The impedance technique has been
used for the measurement of the chlorpyrifos in the soil, tape
water and corn leaves. The impedance increases as the
concentration of the chlorpyrifos increases in the sample and
wide linear range was observed from 20 to 300 mg L1 with
a detection limit of 4.5 mg L1.51
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48
with
3.4. Polycyclic aromatic hydrocarbons
Polycyclic aromatic hydrocarbons (PAHs) are widespread envi-
ronmental pollutants. PAHs have been added into the envi-
ronment by human activities and also by natural incidents like
volcanic eruption, forest res, burning of fossils and the
petroleum fuel. These compounds are considered highly toxic
due to their mutagenic and carcinogenic behavior. The PAHs
carcinogenicity has been related to the number of benzene rings
in their structures and their transformation into the reactive
electrophilic intermediates metabolites. The mammalian
converts these compounds into the detoxication products in
the liver and these metabolized products when excreted are
more genotoxic and reactive. The PAH metabolites are respon-
sible for carcinogenic process by covalently binding to the
cellular DNA. These aromatic compounds become activated in
the presence of sunlight and cellular destruction may start if
skin comes into contact with these compounds in the presence
of light.
3.4.1. 7,12-Dimethylbenz[a]anthracene. One of the PAHs is
7,12-dimethylbenz[a]anthracene (DMBA) that has been widely
investigated for its biological activity. Because of its potential
toxic and carcinogenic effects, many methods have been
developed for its trace level quantitation. Y. Yardım et al.,
developed a highly sensitive method based on the disposable
pencil graphite electrode and also studied the interaction of
DNA and DMBA. The adsorptive stripping voltammetry was
used for the low level determination of DMBA and an LOD of
0.194 nM was achieved.52
3.4.2. Benzo[a]pyrene. One of the potent carcinogenic
polyaromatic compounds is benzo[a]pyrene (BaP). The BaP is
found in coke plants, steel foundries, and aluminum plants.
The places where the coal res is used for heating or cooking
normally contains a higher concentration of BaP. The human
exposure to the BaP occurs through water, foodstuff, and the
air. Like other PAHs, BaP is hydrophobic compound and accu-
mulate in the liver, kidney and the fat tissue. The mammalian
metabolizes BaP with the help of epoxide hydrolase and cyto-
chrome P450-dependent monooxygenase to primary and
secondary metabolites like phenols, diols, quinones, water-
soluble conjugates and arene oxide. BaP concentration in the
environment is correlated to the total content of the PAHs. The
adsorptive stripping square wave voltammetric based method
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Table 3 Applications of GPE based sensors for detection of various organic pollutants in environmental samples

Detection in
Electrode Analyte Matrix Medium/pH Technique Linear range LOD real samples Ref.

pCu/GPE 4-Nitrophenol — 0.1 M acetate Amperometry 50–850 mM 1.91 mM No 40

buffer/4.8
ETGPE Bisphenol A Tap and river 0.1 M PBS/2.0 ASDPV 0.05–5.0, 5–10 mM 0.0031 mM Yes 45
water
DNA/MWCNTs- Chrysoidine Food products 0.5 M acetate DPV 0.05–15.00 mg mL1 0.03 mg mL1 Yes 47
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PDDA/GPE buffer/4.8
MIP/PPy/GPE Sulfanilamide Blood serum, 0.04 M BR buffer/2.0 DPV 5.0
108 to 2.0
108 M Yes 48
ground water 1.1
106 M,
1.1
106 to
48
106 M
PGPE 4-Nonylphenol, Industrial water PBS/7.4 DPV 1.2–94.0 mM, 0.42 mM, Yes 11
4-octylphenol, 0.6–78 mM, 0.25 mM,
4-tert-octylphenol 2.38–243 mM 0.77 mM
MIP/PPy/GPE Chlorpyrifos Tap water, soil, 0.1 M KCl Impedance 20–300 mg L1 4.5 mg L1 Yes 51
corn leaves
PANI/MWCNTs/ Bisphenol A Extracted water 0.1 M glycine– Amperometry 1–400 mM 10 nM Yes 44
GPE from baby bottles NaOH/10.6
Ds-DNA/GPE Sudan II Chili sauce, 0.5 M acetate buffer/ DPV 0.5–6.0 mg mL1 0.4 mg mL1 Yes 49
ketchup sauce 4.8
PGPE Sudan II Chili sauce, 0.1 M PBS/4.8 ASDPV 0.0015–0.30 0.00007 Yes 49
ketchup sauce mg mL1 mg mL1
GPE Thiourea Waste water PB/12.0 SWV 6.3–30 mM 1.29 mM Yes 86
Ds-DNA/GPE 7,12-Dimethylbenz- Urine 0.1 M acetate SWSV 2–10 nM 0.194 nM Yes 52
[a]anthracene buffer/4.8
PGPE Benzo[a]pyrene Urine 0.1 M acetate buffer/ ASWV 0.25–1.25 mM 0.027 mM Yes 53
4.8

was established by E. Keskin et al. using pretreated pencil
graphite electrode for the determination of BaP. A small linear
range has been observed from 0.25 to 1.25 mM with low detec-
tion limit 0.027 mM. The developed method was applied to nd
out the spiked BaP from the urine and satisfactory values for
recoveries were obtained.53 Table 3 lists applications of GPE
based electrodes for detection of organic analytes in different
environmental matrices.
4. A brief overview of materials used
for modification of GPE
In order to enhance their electrocatalytic activity toward certain
inorganic or organic analytes, GP based electrodes were modi-
ed with different materials. These modication materials
include metal nanoparticles, conducting polymers and carbon-
based materials. In the following sections, we have discussed
modication materials and their potential to increase electro-
catalytic activity.
4.1. Nanoparticles
Nanoparticles (NPs) are characterized by their better physical,
chemical, and electronic features than their bulk counterparts.
It is the nature of the material used for synthesis that deter-
mines properties of NPs. Commonly, NPs are synthesized by
chemical reduction of metal salts in the presence of a stabilizer.
Stabilizers are attached to the surface of NPs and play a major
role in dening their charge, solubility, and stability. NPs are
extremely sensitive to the changes occurring on their surface.
NPs modied electrodes may result in enhanced electron
kinetics due to following
(i) High surface area.
(ii) Enhanced mass transport rates.
(iii) Better control of NP surface.
(iv) Functionalization of NPs with selective groups.
Recently, metal NPs (MNPs) have drawn signicant attention
in electrocatalysis because of their unique chemical and elec-
tronic conduct. The analytes that show sluggish electron
kinetics at bare electrodes were reported to have reasonably
enhanced electrocatalytic activity at MNP's modied electrodes.
In addition, MNPs modied electrodes showed good peak
separations for compounds having very close oxidation
potentials.
Recently, the very simple procedure was adopted for immo-
bilization of Au NPs on GPE for detection of hydrazine. The
beauty of this modication is in the process that involves direct
attachment of Au NPs on the surface of GPE without the use of
any cross-linkers. Fig. 3 shows SEM images of Au NPs modied
GPE at different magnication levels, and Fig. 4 clearly shows
enhanced response at Au NPs modied GPE compared to bare
GPE for detection of hydrazine.12 Similarly, in another report,
platinum modied GPE was synthesized by one-step reaction
that involves reduction of metal salt while dipping the GPE in
reaction media.30 There are some examples where MNPs are
used in combination with other materials such as CNTs. Such

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Fig. 3FE-SEM images at two different magnifications, 2 mm and 200 nm of gold nanoparticle-modified GPE. Modified and reprinted from 12 with
permission. Copyright 2013 Elsevier.
combinations are thought to contribute to sensing properties of
electrodes through synergistic effect.
4.2. Conducting polymers
Different types of polymers are used in electrochemical sensing
applications. Overall, these polymers can be categorized into
four classes i.e. electroactive, polyelectrolyte, coordinating and
biological polymers. The selection of a certain polymer for
electrode modication is mainly dictated by the nature of the
target analytes. The electrodes can be modied with polymers
using different strategies. The frequently used methods include
spin coating, dip coating, and electropolymerization. Conduct-
ing polymers allow the incorporation of counter ions or other
functional moieties into the structure of polymers. In this way,
modied electrodes can be made selective against target ana-
lytes. Their electronic properties have similarity with metals.
The polymer coated electrodes can help in avoiding interfer-
ences because selective coating materials will distinguish
between the analyte and other species via hydrophilic and
Fig. 4 CVs in 0.1 mol L1 PBS (pH 7) in the absence (A) or presence (B)
of 0.5 mmol L1 hydrazine at a bare GPE (a) and at a AuNP-GPE (b).
Scan rate: 100 mV s1. Modified and reprinted from12 with permission.
Copyright 2013 Elsevier.
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hydrophobic interactions, electrostatic affinities and ion
exchange capabilities.
The use of Ponceau 4R azo dye doped polypyrrole modied
GPE for selective potentiometric determination of Cu2+ in water
is an example of the polymer based ion selective electrode. In
this work, the pyrrole monomers were electrochemically poly-
merized on GPE in the presence of Ponceau 4R azo dye as
a dopant. The application of dopant in electropolymerization
generates selective recognition sites in the coating which
interact selectively with Cu2+ ions.22 Similarly, there are
numerous other examples where polymer modied GPEs were
employed as ISE for analysis of different metals.15,19,23 MIPs48
and polymer nanocomposites33,44 are also used for modication
of GPE for different sensing applications.
4.3. Carbon nanotubes
Carbon nanotubes (CNTs) have gained a great attraction since
its discovery in 1991 by Iijima. CNTs being a sp2 allotrope of
carbon could be divided into two types (a) single-wall carbon
nanotubes (SWCNTs) and (b) multiwall carbon nanotubes
(MWCNTs). SWCNTs could be considered as the rolling of the
single layer graphene while MWCNTs is the rolling of the
multilayer graphene.54 SWCNTs and MWCNTs could be
synthesized by vapors deposition methods, electrical arc
discharge, and laser vaporization.55 The rapid development has
been witnessed in the fabrication of the CNTs based sensor
from past few years. Many studies have been reported in which
CNTs based sensors has shown great electrocatalytic properties
towards analytes. CNTs are considered as good electrode
material due to fast charge transfer and also shown the
compatibility and synergistic effect with the other electrode
materials.54
H. Safardoust-Hojaghan et al. has introduced a new device
consist of puried MWCNTs and Bi NPs nanocomposite which
was immobilized on the surface of GPE. The response of the Bi
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NPs modied GPE was increased by adding the puried
MWCNTs. The MWCNTs increased the surface area with Bi NPs
and facilitated the fast charge transfer. The electrochemical
impedance study has shown the MWCNTs with Bi NPs have
reduced the charge transfer resistance signicantly.17 In
another work, the MWCNTs was used in combination with
electroactive polymer poly(vinyl ferrocenium). PVF+/MWCNTs/
GPE was fabricated by single step electrooxidation of PVF/
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MWCNTs at +0.7 V for determination of nitrite. MWNCNTs
and poly(vinyl ferrocenium) have increased the sensitivity of the
GPE electrode for nitrite determination compared to bare GPE
and PVF+/GPE.33 MWCNTs were also used for the GPE based
biosensors. A. Ensa et al. reported work in which dsDNA was
immobilized on the surface of MWCNTs-PDDA/GPE to develop
a biosensor for the sensitive sensing of banned dye, chrys-
oidine. PDDA is a positive charge electrolyte which adsorbs or
wraps the MWCNTs when sonicated together. This process
leads to positive charge nanocomposite which provided a good
effective surface area for the loading of dsDNA.47 In another
work, the MWCNTs with polyaniline nanorods was used for the
surface modication of the GPE. PANI rods alone on the GPE
surface has given broad and low oxidation peak current
compared to MWCNTs which describes MWCNTs has more fast
charge transfer capability. The combination of both PANI and
MWCNTs has shown excellent sensitivity towards bisphenol A.44
4.4. Pretreatment
This is a very common method to enhance the sensitivity of
the carbon-based electrodes. This method is widely being
used for increasing the sensitivity of the graphite pencil
electrode. During electrochemical pretreatment, the electrode
surface was cleaned, and some oxygen-containing groups also
formed on the surface of GPE. The enhancement of the
current could be attributed to the formation of oxygen-
containing functional groups like carboxylic acid, phenolic,
and carbonyl. In this process might be some graphite oxide
lms are also formed on the GPR surface which is also
responsible for the current enhancement for the target ana-
lytes.56 Electrochemical pretreatment is attractive choice due
to the following reasons.57
 Very simple.
 Less time-consuming.
 No complex material required.
 More applicable compared other modication materials.
For pretreatment, the number of electrolytes is being used
like NaOH, the pretreated electrode was used for the determi-
nation of Sudan.49 E. Keskin et al., pretreated the pencil elec-
trode by dipping the electrode in DMSO/0.1 M LiClO4 mixture at
+1.6 V for sensing of benzo[a]pyrene.53 Recently, the surface of
the graphite pencil electrode was charged by pretreating the
GPE in NaOH solution. The charged surface was used for the
self-electropolymerization of the phenol on the electrode
surface for the sensitive sensing of phenol. It is a very simple
method for the determination of phenol.37 The effect of
different pretreatment solutions on the response of GPE surface
charging for detection of phenol is shown in Fig. 5.
91336 | RSC Adv., 2016, 6, 91325–91340
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Review
Fig. 5 (A) SWVs obtained from a 2 mM phenol solution in 0.1 M
phosphate buffer, pH 7.2, in the presence of the uncharged (a) and
charged GPEs in various 0.1 M media: (b) NaCl, (c) HCl, (d) Na2HPO4,
and (e) NaOH solutions. (B) The corresponding histogram. Repro-
duced from37 with permission Copyright 2016 WILEY-VCH Verlag
GmbH & Co. KGaA, Weinheim.
5. Comparison of GPE with other
electrodes
Graphite pencil electrode is still an emerging electrode. There
are few characteristics which make it unique over other carbon
and metallic based electrodes and a good candidate for elec-
trochemical sensing.
This single use electrode has the advantage to make the
surface foul free.37,58 Any electrode could be a single use elec-
trode, but the cost is an issue. Glassy carbon electrode (GCE), Au
and Pt disc electrode could not be employed as disposable
electrodes due to high cost and their manufacturing style. Due
to this reason, GCE, Au, and Pt disc electrodes are being used
for multiple times aer polishing the surface by number of
different ways to get rid of adsorbed materials and to improve
the electrochemical behavior.59–61 GPE could be a single used
electrode as the new surface is readily available aer the
measurement. However, screen printed electrode (SPE) is well
established single use electrode, but it is costly compared to
GPE. SPE surface cleaning is usually not required, but polishing
could have some positive effect.62 For carbon paste electrode
(CPE) fabrication, a typical preparation is needed which is time-
consuming.63
Control of sensing area is another attractive characteristic
which is associated with GPE58 and it is not much feasible for
GCE, CPE and the SPEs where the active surface is provided by
the supplier. In case of GPE the length of the extruded graphite
pencil could be adjusted according to the requirement.
Recently, the GPE was used for the sensing of a-naphthol. The
response of the bare GPE towards a naphthol was compared
with GCE, CPE, Au and Pt disc electrode and it was more
sensitive.64 Casting modication of GPE is difficult and chal-
lenging due to its elongated shape and small diameter
compared to GCE, CPE, SPE, Au and Pt disc electrode.
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Table 4 Comparison of different characteristics of GPE with other electrodes

Sr# Characteristic GPE GCE CPE SPE Au disc E Pt disc E

1 Availability Easily available Easily available Need preparation Easily available Easily available Easily available
2 Cost Very cheap Costly Average cost Costly (due to Costly Costly
single use)
3 Disposable (single use) Yes No No Yes No No
4 Surface polishing Not required58 Required59 Required (removal Not required Required60 Required61
and smoothing
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of surface)63
5 Control of sensing area Yes No No No No No
6 Sensitivity (a-naphthol) Very good64 Good64 Good64 — Low64 Low64
7 Casting modication Difficult Easy59 Easy87 Easy88 Easy89 Easy90
8 (Modications)/LOD (Pd NPs-GPE)/ (Pd NPs-GCE)/ (HRP-Au NPs/ (Pt–PdBNC/ ((MWCNT/Ag —
analyte (H2O2) 0.045 mM 31 0.34 mM 65 CCPE)/6.3 mM 66 SPGFE)/0.87 mM 67 nanohybrids)
modied gold
electrode)/0.5 mM 60

The comparison of LODs for the detection of same analyte at
different bare and modied electrode is nearly impossible task.
The similar modications of various electrodes can give real
insight of the sensitivity of the electrodes toward certain analy-
tes. However, it is rare to nd similar modication on all elec-
trodes for detection of same analyte. Moreover, the LOD of the
H2O2 sensing on the different modied electrodes is compared
(Table 4). While making this comparison, it was tried to choose
the modication as similar as possible. Pd NPs/GPE has shown
good response towards H2O2 (ref. 31, 60 and 65–67) compared to
closely modied electrodes. All these characteristics made GPE
a valuable electrode for electrochemical sensing.
5.1. Attractive features and challenges of graphite pencil
electrodes
GPE possesses many attractive and unique features which make
it an excellent choice for electrochemical sensing. These
features are summarized below.
 A unique feature is the provision of the renewable surface
aer each measurement68 just like the dropping mercury elec-
trode. This feature makes the electrode surface foul free. But in
the case of most of other electrodes like GCE, aer each elec-
trochemical measurement, a number of by-products are formed
which can adhere to the surface of the electrode and could
compromise the sensitivity of the electrode. However, here in
case of GPE, the part of the used electrode can be easily
removed, and the new surface is readily available.
 The surface polishing is generally not required prior to
use.69
 The GPE is easily available70 as it is widely used for writing
purposes as a graphite pencil.
 It is also disposable70 like screen-printed electrode.
However, it is extremely low cost71 compared to disposable SPE.
 Handling of GPE is relatively easy, and due to its elongated
shape, the direct electro-modication methods are more
facile.72
 GPE is found more sensitive compared to GCE64,71 (greater
sensitivity is due to the presence of porosity on the surface of
GPE).
 The control of the sensing area is also possible by changing
the extruded pencil length.
Despite its excellent behavior and the advantages, the GPE is
facing few problems. Still, it is not a well-established electrode,
and it is not prepared for electrode applications, due to this
reason, sometimes the electrode composition may vary. This
could affect the sensor behavior. Such issues can be xed by
preparing the graphite pencil typically for electrode purposes.
The modication by casting method is also challenging due to
the smaller diameter of a pencil.
Although there are some challenges associated with GPE, the
GPE can be an excellent commercial electrode due to the above
attractive features for the study of environmental pollutants. It
has the capability to overcome the regeneration problem of the
other solid state electrodes.69
6. Future scope and outlook
Point of care (POC) testing has become the most well-known
way of diagnosis in clinical analysis, food safety, and the envi-
ronment. The main advantage of POC lies in the fact that it
provides results in very short time compared to centralized
laboratories. These devices are helpful in making quick
decisions.
The water that is considered to be a matrix of life has been
highly polluted with inorganic and organic impurities in
different parts of the globe due to the industrial revolution. This
fact has already been indicated by a number of published
reports.73. Similarly, thousands of publications talk about
analytical method development for analysis of inorganic and
organic pollutants in water, food74 and biological samples.75
However, POC like devices that can readily analyze water or
other environmental matrices for the presence of inorganics or
organics is still not available to the public. Hence, there is very
high stress on existing analytical technologies to meet the
demands of low cost, availability, sensitivity and applicability in
on eld analysis.
GPE based electrochemical devices can have the potential to
serve in POC applications. Their low cost, easy availability, and

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RSC Advances Review

trait of disposability make them quite t for POC based devices. of certain analytes in environmental matrices. The miniatur-
Despite low cost and commercial availability of GP based elec- ized devices at mass level can only be generated by the inte-
trodes, the commercialization of readily available GPE sensors gration between electronics, electrochemistry, electrical
for real life samples is still at some distance from the reality. engineering and analytical chemistry.
Every lab prepared prototype cannot be brought to the market
without considering its suitability for the desired assay, study of Abbreviations
consumables and acceptability by the consumers. Although
electrochemical methods involving modied GPEs demonstrate
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a grade of maturity good enough to implement them in real PSS/CnP/GPE Polystyrenesulfonate/carbon nanopowders/
analytical applications but up till now, their applications are pencil graphite electrode;
limited to proof of concepts. For a proof of concept, different Ag/FeOOH/GPE Silver/FeOOH/GPE
materials such as nanoparticles, conductive polymers, and PtNPs/GPE Platinum nanoparticle-modied GPE
carbon-based materials have been used to modify the surface of Hb/PLE Hemoglobin/modied pencil lead electrode
PVF+/MWCNTs/ Poly(vinylferrocenium)/multi-walled carbon
GPEs. However, which of them can be employed for mass
GPE nanotubes/GPE
production of modied GPEs for certain analysis will be
Bi-NPs/ Bismuth NPs/puried multiwalled carbon
dictated by cost, ease of synthesis and stability of the material
puMWCNT/GPE nanotubes/GPE
over the electrode surface. Moreover, the integration of such
NG/PG/BiE Naon graphene/pencil graphite/bismuth
modied electrodes into miniaturized systems is nothing less
lm electrode
than a challenge as commercialization needs careful designing Poly(PyY)/GPE Poly pyronin Y/pencil graphite electrode
of the product that should be compatible with market demands. Cu-P4R/PPy/GPE Copper-Ponceau 4R azo dye/polypyrol/GPE
Thus, these challenges need to be addressed in future. Au NPs/GPE Gold nanoparticles/GPE
P4VP/GPE Poly(4-vinyl pyridine)/GPE
7. Conclusive remarks DPC/PANI/GPE Diphenylcarbazide/polyaniline/GPE
Cu–Car/PA/GPE Carmoisine–Cu(II) complex/polyaniline/GPE
In the area of environmental analysis, a growing variety of low- (HRP/AuNPs)2/ Horseradish peroxidase/gold nanoparticles/
cost analytical sensors is always welcomed. Useful sensors are CS/GPE chitosan/GPE
recognized not only by their cost but the simplicity of fabri- Tar/PPy/GPE Tartrazine/polypyrrole/GPE
cation and operation. The sensors which can serve in point of pCu/GPE Porous copper/graphite pencil electrode
care or in eld applications even for qualitative or semi- ETGPEE Electrochemically treated pencil graphite
quantitative analysis are paramount for elevating the quality electrode
of life through quick analysis.76 GPE based electrodes have MIP/PPy/GPE Molecular imprinted polymer/polypyrol/
been widely used for quantitative determination of inorganic graphite pencil electrode
and organic, environmental pollutants. GPEs are inexpensive PGPE Pretreated pencil graphite electrode
and commercially available electrodes that can compete with PANI/MWCNTs/ Polyaniline nanorods/multiwalled carbon
other expensive metallic and non-metallic electrodes. GPE GPE nanotubes/GPE
offers renewable surface, which can be easily modied with LOD Limit of detection
AFS Atomic uorescence spectroscopy
a number of materials including nanoparticles and conduct-
FAAS Flame atomic absorption spectroscopy
ing polymers, CNTs, and pretreatment. Modication of GPE
GFFAAS Graphite furnace atomic absorption
with nanomaterials or direct formation of NPs on GPE surface
spectroscopy
enhances its surface area, which in turn, results in high
ISE Ion selective electrode
sensitivity and improved electrochemical activity toward
HRP-Au NPs/ Horseradish peroxidase-gold nanoparticles/
detection of target species. GPE based electrodes are easy to CCPE chitosan carbon paste electrode
miniaturize. Due to high selectivity and sensitivity, portability, Pt–PdBNC/ Pt–Pd bimetallic nanoclusters/screen-
rapid analysis, and ease of availability, GP based electrodes SPGFE printed gold nanolm electrode
offer excellent opportunities for decentralized environmental AuNPs/AG/SPCE Gold nanoparticles/activated graphite/
analytical labs. These electrodes can also provide an oppor- screen printed carbon electrode
tunity for the development of low-cost commercially available
sensors for analysis of a number of analytes in the environ-
ment, e.g., customers by themselves can monitor toxic metals
in their drinking water. Although, GPE based electrodes got
Acknowledgements
a high degree of maturity from fabrication and modication The authors acknowledge the support provided by King Fahd
point of view, but still they are at a signicant distance from University of Petroleum and Minerals for funding this work
commercialization. The leading challenge, however, is to through project no. SB141010.
bring these GPE based electrochemical techniques in the
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