Trends Trends in Analytical Chemistry, Vol. 30, No.

11, 2011

Nanoparticles in electrochemical
sensors for environmental
monitoring
Liza Rassaei, Mandana Amiri, Ciprian Mihai Cirtiu, Markus Sillanpaa,
Frank Marken, Mika Sillanpaa

We review the state-of-the-art application of nanoparticles (NPs) in electrochemical analysis of environmental pollutants. We
summarize methods for preparing NPs and modifying electrode surfaces with NPs. We describe several examples of applications
in environmental electrochemical sensors and performance in terms of sensitivity and selectivity for both metal and metal-oxide
NPs. We present recent trends in the beneficial use of NPs in constructing electrochemical sensors for environmental monitoring
and discuss future challenges.
NPs have promising potential to increase competitiveness of electrochemical sensors in environmental monitoring, though
research has focused mainly on development of methodology for fabricating new sensors, and the number of studies for
optimizing the performance of sensors and the applicability to real samples is still limited.
2011 Elsevier Ltd. All rights reserved.

Keywords: Air pollution; Amperometry; Electrochemical sensor; Environmental monitoring; Heavy metal; Herbicide; Modified electrode;
Nanoparticle; Pesticide; Voltammetry

1. Introduction Heavy metals occur naturally in the

Liza Rassaei* environment, but, due to industrialization,
MESA+ Institute for
Nanotechnology, University of
Monitoring air, soil and water for haz- large amounts of heavy metals bound in
Twente, Enschede, ardous pollutants is important and based fossil fuels and mineral materials have
The Netherlands on the need to protect the environment been released into the environment and
and public health from possible distribu- deposited in trace amounts in nearly every
Mandana Amiri
Department of Chemistry, University tion of natural and industrial inorganic part of the planet. Elevated levels of heavy
of Mohaghegh Ardabili, Ardabil, Iran and organic contaminants. There is a metals in natural water may have a det-
constantly increasing need for online rimental effect on both human health and
Ciprian Mihai Cirtiu
Department of Chemistry, McGill
monitoring of contaminants in our envi- the environment [1]. Apart from the direct
University, 801 Sherbrooke Street ronment, driven by new legislation and impact on health or environmental prob-
West, Montreal (PQ) H3A 2K6, new technologies. Important examples are lems, water or soil contamination can
Canada
(i) control of wastewater quality to avoid cause considerable economic and financial
Markus Sillanpaa release of synthetic drugs residues or damage, so there is a need for novel
Research and Innovation Laboratory, detergents and (ii) monitoring of persistent instruments capable of real-time, in-situ
Finnish Environment Institute, P.O.
carcinogens or residues of explosives re- detection of heavy metals and online
Box 140, FI-00251 Helsinki, Finland
leased into the environment. monitoring.
Frank Marken Pesticides (herbicides, fungicides and Air pollution is another serious problem,
Department of Chemistry, University insecticides) are widely used in agriculture especially in many heavily populated and
of Bath, Bath BA2 7AY, UK
and industry. To limit their toxicity and industrialized areas, and in newly devel-
Mika Sillanpaa their accumulation in living organisms, oping countries. In the majority of the
Laboratory of Green Chemistry, LUT dose adjustment and trace-level monitor- developed world, legislation has already
Energy, Lappeenranta University of
ing are desirable. Thus, there is an essen- been introduced to an extent that local
Technology, Patteristonkatu 1,
50101 Mikkeli, Finland tial need to develop new methods for authorities are requested by law to con-
simple pesticide detection at low concen- duct regular local air-quality monitoring
*
trations, especially in the field. of major urban pollutants (e.g., ozone,
Corresponding author.
E-mail: [email protected]

1704 0165-9936/$ - see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.trac.2011.05.009
Trends in Analytical Chemistry, Vol. 30, No. 11, 2011 Trends

benzene, SO2, CO, CO2 and NOx produced by industrial optical, catalytic and magnetic properties as well as their
activity and transportation) [2]. In order to achieve this extremely high surface area per mass. In addition to
goal, pollutant concentrations must be monitored novel properties, nanomaterials and nanotechnology
accurately, and ideally in situ, so that sources may be open up new approaches to manufacture electrodes cost
recognized quickly and the atmospheric dynamics of the effectively by minimizing the materials needed and waste
process are understood. Growing concern worldwide generation [5]. This is especially relevant to expensive
about air pollution and its effect on the environment, materials (e.g., gold and platinum). For example,
industrial safety and hygiene has also made it essential inexpensive materials (e.g., carbon coated by NPs) result
to monitor gaseous species (e.g., SO2, H2S, ozone, H2, in a large ratio of surface area to volume for low-cost
NOx, CO, Cl2, NH3, formaldehyde, ethanol, propane or sensing electrodes. In recent studies, it was demonstrated
ethylene oxide). Furthermore, such data would lead to that NP electrodes could be obtained with high sensi-
real-time environmental decision-making capabilities as tivity and even with individual NPs giving responses
a result of hazardous levels being rapidly identified [2,3]. [6,7].
Increasing concern about the distribution and the The combination of nanotechnology with modern
impact of chemical reagents from analytical methodol- electrochemical techniques allows the introduction of
ogies has led to new field methods designed to minimize powerful, reliable electrical devices for effective process
use of toxic reagents during sample pretreatment and and pollution control. Although the NPs in general play
analytical measurement. Electrochemical methods for different roles in different electrochemical sensors, with
analysis can be especially sensitive, cheap and portable regard to electroanalysis using a NP-modified electrode
to provide data even in remote locations. A wide range of has several advantages:
electrochemical sensors that fulfill the requirement to be (1) effective catalysis;
environment friendly are commercially available. For (2) fast mass transport;
example, sensors for water monitoring have been (3) large effective sensor surface area; and,
developed, and several of these are now advanced pro- (4) good control over electrode microenvironment [5].
totypes. Electrochemical monitoring is especially of NPs also present attractive characteristics often nota-
interest for in-situ measurements with simple, compact bly different from bulk materials in terms of both phys-
and mobile equipment. ical and chemical features. However, while several
Typical electrochemical sensors comprise a sensing nanomaterial-based sensor systems have been reported
electrode (as transduction element), a diffusion barrier, a in the literature, their implementation in routine in-situ
counter-reference electrode and an electrolyte. The devices remains a challenge. The monitoring of indus-
analytical information is obtained from the electrical trial processes with known sample matrix is usually
signal that results from the interaction of the target accurate and reliable; however, in-situ monitoring in
analyte and the recognition layer at the sensing elec- environmental analysis often with an unknown or
trode. Depending on the electrical signal to be measured, changing matrix provides a bigger challenge in the
electrochemical techniques are divided into potentio- development of measurement devices [8]. Electrochemi-
metric, conductometric, amperometric or voltammetric cal sensors have been employed for several decades for a
methods. Different electrochemical devices have been variety of environmental monitoring applications,
developed for environmental monitoring, depending on including monitoring of water-quality parameters (con-
the nature of the analyte, the characteristics of the ductivity, dissolved oxygen or pH) [9], measurement of
sample matrix and sensitivity or selectivity requirements. trace heavy metals [10], and carcinogens and organic
The ideal sensor should possess the following charac- pollutants (N-nitroso compounds, aromatic amines and
teristics [4]: phenols) [11]. There is a myriad of different NP materi-
(1) specificity for the target species; als, but they are usually divided by their chemical nature
(2) sensitivity to changes in target-species concentra- into six groups:
tions; (1) metals;
(3) fast response time; (2) metal oxides;
(4) extended lifetime of at least several months; and, (3) carbonaceous;
(5) small size (miniaturization) with the possibility of (4) polymeric;
low-cost manufacture. (5) dendrimeric; and,
Nanoparticles (NPs) are attracting attention due to (6) composites.
their low cost and unique size-dependent properties. The Most relevant in the design of electrochemical sensors
incorporation of NPs into a variety of matrices to form are metal and metal-oxide NPs, so these provide the
nanocomposite films is attracting much attention. NPs focus of this review. A further topic developing from the
have been used in many electrochemical, electroana- wider use of nanotechnology (not covered in this review)
lytical and bioelectrochemical applications. The is the environmental impact and potential health effects
uniqueness of NPs is due to their mechanical, electrical, of NPs, which are still largely unknown.

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Trends Trends in Analytical Chemistry, Vol. 30, No. 11, 2011

Although several review articles have addressed the most important characteristics of NPs for their perfor-
application of NPs in electroanalysis [3,4], their appli- mance in electrochemical-sensor design, because,
cations as sensing elements in electrochemical analysis depending on the size and the distance between adjacent
for environmental monitoring have not previously been particles, the degree of diffusion-layer overlap (the nature
the focus, so the aim of this review is critically to assess of the voltammetric responses) can be manipulated [14].
and to overview the role of NPs used in the design of Defined and ordered arrangement of NPs is a promising
electrochemical sensors for environmental monitoring. approach for the construction of electrochemical sensors.
The intention is not to provide a complete, exhaustive The electrode surface can be modified with colloidal
review of the available literature, but rather to provide NPs by simply casting a mixture of NPs and additives
insight into potential applications and benefits of NPs for (e.g., an enzyme). Methods have been developed with
electrochemical environmental monitoring. First, we solvent evaporation, growth of an NP-modified sol-gel
introduce different methods of NP preparation, then we network on the electrode surface, or electro-aggregation.
address electrode-surface modification and sensor prep- NPs can be modified with different functional groups and
aration, and finally we describe the application and the then immobilized on the electrode surface. It is possible
performance for several examples of reported NP-based to pre-mix the NPs with conductive materials (e.g., dif-
sensors for environmental monitoring. ferent types of nano-carbon to prepare a paste electrode)
or to trap them in a conductive polymer. The layer-by-
layer method based on electrostatic interaction has been
2. Preparing nanoparticles and modifying used for charged NPs, which get entrapped in an oppo-
electrode surfaces sitely-charged poly-electrolyte [15]. In many cases, by
applying a reducing potential, NPs are directly electro-
2.1. Colloidal nanoparticles deposited from the appropriate salt solutions onto the
The development of newer methods for the controlled electrode surface so as to have the desired size. These NP-
synthesis of metal NPs with different shapes and sizes deposition processes are easy to use, although control of
has attracted attention during the past decade. One of the size of the particles may be greatly depend on
the advantages of using NPs in sensing design is that deposition time, deposition potential, electrolyte solution,
their size and their surface characteristics can be tuned and the salt concentration. Fig. 1 shows typical SEM
during the preparation process to achieve high sensi- images illustrating the effect of electrodeposition time on
tivity or selectivity. The preparation methods for NPs the morphology and the density of Au-NPs on boron-
have been reviewed [12]. Different wet chemical meth- doped diamond (BDD)-electrode substrates [16]. It can be
ods have been used for the synthesis of metallic NP seen that the longer the deposition time, the larger the
dispersions. The most commonly employed techniques average diameters of deposited Au-NPs. With the depo-
involve the use of excess reducing agents (e.g., sodium sition time of 10 s, 30 s and 60 s, Au-NP diameters were
citrate, tannic acid or NaBH4). NPs can also be synthe- reported as 79.5 11.3 nm, 152.8 11.4 nm, and
sized in a two-phase water-organic system, or using an 222.8 18.3 nm, respectively. At the deposition time of
organic reducing agent (e.g., aldehydes) or reverse mi- 600 s, the Au-NPs deposited in a multilayer cluster after
celles. The concentrations of the salt and the reducing covering all BDD surfaces. In general, NPs are prefer-
agent and temperature are important parameters to entially deposited on the substrate defects or at the edges,
determine the size of NPs. Finally, NPs can be prepared resulting in a non-uniform distribution [17]. Therefore,
by unconventional methods (e.g., radiolysis, laser abla- using pre-synthesized and functionalized colloidal NPs
tion, vacuum evaporation, or microwave techniques). may solve some of these problems when well-defined
Metal-oxide NPs are prepared based on chemical nanostructured deposits are needed.
methods (e.g., hydrolysis) and physical methods, When the electrode surface is modified using electro-
including sputtering, evaporation (thermal and electron deposition techniques, the pH or the electrode potential
beam), pulse-laser deposition and ion implantation. applied may cause unwanted dissolution or formation of
Assemblies of NPs can be prepared by using chemical surface oxides on the electrode surface. Cu-NPs and Ni-
techniques [e.g., sol-gel, co-precipitation, impregnation, NPs are oxidized easily so their formation on the elec-
or chemical-vapor synthesis (CVS)] or hydrothermal trode surface can also be carried out in situ.
techniques. There have been reviews on growth of NPs
in gas and liquid phases [13].
3. Electrochemical characterization of
2.2. Modification of the electrode surface with nanoparticle-modified electrodes
nanoparticles
Various attachment techniques, including physical and 3.1. Methods
chemical methods, are commonly used for the deposition Compared to bulk electrodes, the presence of NPs on the
of colloidal NPs. Particle size and size distribution are the electrode surface enables fast electron-transfer kinetics,

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Trends in Analytical Chemistry, Vol. 30, No. 11, 2011 Trends

Figure 1. SEM images of a polycrystalline boron-doped diamond (BDD) electrode surface after direct electrochemical Au-NP deposition:
deposition time of (a) 10 s, (b) 30 s (c) 60 s and (d) 600 s [16] (reprinted with permission from Elsevier).

reduces overpotential, increases the electro-active sur- Electrochemical impedance spectroscopy (EIS) can also
face area, and causes redox reactions to become be employed to investigate the changes in impedance of
kinetically feasible [5]. From electrochemical studies of the electrode surface as a function of coverage for
NP-modified electrodes, it is possible to calculate the NP-modified electrodes. Fig. 2C shows typical electro-
number of NPs deposited on the electrode surface, chemical-impedance spectra of the [Fe(CN)6]3/
capacitive charging effects or specific underpotential [Fe(CN)6]4 redox couples for unmodified and modified
deposition (UPD) effects. Many NPs, including Au-NPs electrodes with Pd-NPs. It can be observed that the
and Pt-NPs, are electrochemically-active materials. They semicircle diameter of the Nyquist plot for [Fe(CN)6]3/
possess distinct electrochemical properties because of [Fe(CN)6]4 redox has significantly changed with the
their unique electronic structures. Fig. 2A shows typical loading of Pd-NPs on the substrate [21]. The apparent
cyclic voltammograms of an indium tin oxide (ITO) standard heterogeneous rate constant (assuming
electrode before and after Pt-NPs were grown onto the [Fe(CN)6]3 = [Fe(CN)6]4) is obtained using [22]
surface [18]. k app RT =F 2 Rct AC  where Rct, T, F, A and C* represent
Due to the simple, well-defined responses, redox the gas constant, the absolute temperature, the Faraday
models (e.g., the [Fe(CN)6]4/[Fe(CN)6]3 or constant, the true area and the bulk concentration of the
3+ 2+
Ru(NH3)6 /Ru(NH3)6 couples) have been widely used redox couple, respectively [22]. Generally, the kapp values
to characterize the surface properties of different NP- for the [Fe(CN)6]3/[Fe(CN)6]4 redox couple on NP ar-
modified electrodes (see Fig. 2B) [19]. The voltammetry rays prepared under different growth conditions indicate
of these two standard redox processes is examined in increasingly facile heterogeneous electron-transfer
order to investigate how the NP-surface coverage and kinetics, mainly resulting from an increase in active
electron-transfer kinetics are compared to unmodified area.
electrodes. The electrochemical properties of NP-modi- For environmental monitoring, NPs are mostly used in
fied electrodes significantly depend on their surface two different ways in constructing electrochemical sen-
properties. In cyclic voltammetry experiments, the peak- sors:
to-peak separation and electron-transfer kinetics of NP- (1) together with an enzyme (enzymatic sensors) to in-
modified electrodes have been shown to change with the crease the rate of electron transfer and to improve
amount of NPs. However, there is an optimal coverage the sensitivity of the enzyme; or,
for the amount of NPs on the surface. An excess amount (2) as individual catalysts (non-enzymatic sensors) to
of NPs usually gives no further improvement or in- catalyze the reactions and to lower the limits of
creases the resistance and the double-layer capacitance detection (LODs).
of the modified electrode, leading to a decrease in elec- As their function in these sensors is different, these
trochemical sensitivity [20]. two cases are discussed separately.

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Trends Trends in Analytical Chemistry, Vol. 30, No. 11, 2011

3.2. Enzymatic sensors porating enzymes with nanomaterials combine the rec-
A combination of enzymatic reactions with electro- ognition and catalytic properties of enzymes with the
chemical methods allows development of selective en- electronic properties of NPs. The NPs can help enlarge
zyme-based electrochemical biosensors for determination the enzyme loading at the electrode surface. The NPs
of environmental pollutants. These sensors, although with smaller size (12 nm) have been shown to be
less robust, exhibit good selectivity, sensitivity, rapid more suitable for enzyme immobilization and they in-
response, and have miniature size. In environmental crease the biosensor performance because the small size
monitoring, enzyme-based or protein-based NP sensors of these NPs results in a significant surface-to-volume
have mostly been prepared for detection of pesticides ratio and creates more binding sites on the electrode
(e.g., phenolic compounds) or NOx compounds. A major surface for easier contact with enzyme molecules and
challenge to develop such sensitive and stable sensors less denaturation [23]. NPs of small size also allow more
comes from the effective immobilization and electrical freedom in orientating adsorbed proteins, or they intro-
connection of enzymes to solid electrode surfaces. The duce conducting channels between the prosthetic groups
most promising areas for the use of enzyme electrodes in within the enzyme and the electrode surface. In other
environmental monitoring are pesticide biosensors. En- words, they maximize the utilization of the bioactive sites
zyme electrodes have been investigated as emerging of the enzyme and act as electron-transfer pathways
sensors for faster, simpler detection of pesticides. How- [23]. Due to their high surface area and good biocom-
ever, their sensitivity is not yet adequate for application patibility, surface-functionalized NPs are suitable for
in detecting very low concentrations of pesticides. many surface-immobilization mechanisms, providing a
External supply of substrate is often required to measure suitable support to adsorb redox enzymes and proteins.
the changes in enzyme activity. NPs of appropriate design can adsorb redox enzymes and
Compared to free enzyme in solution, immobilized proteins without loss of biological activity. Moreover,
enzyme can be more stable and resistant to various since most of the NPs carry charges, they can also
environmental changes. Electrochemical sensors incor- electrostatically adsorb biomolecules with opposite

Figure 2. (A) Cyclic voltammograms (scan rate of 50 mV/s) recorded in the solution of H2SO4 for (a) a bare ITO electrode and (b,c) the Pt-NPs-
ITO electrode prepared via (b) 4 and (c) 24 h of growth for a geometric area of 0.031 cm2 [18]. (B) Cyclic voltammograms (scan rate 50 mV/s) of
K3[Fe(CN)6] at bare Au electrode (radius of 1.5 mm) and Au-NPs on GCE (radius of 1.5 mm) [19], and (C) Nyquist diagrams (Z vs. Z) for the EIS
measurements (Amplitude: 5 mV) in 5 mmol/L K3Fe(CN)6/K4Fe(CN)6 in 0.1 mol/L PBS at E1/2 = 0.13 V vs. Ag/AgCl for the bare GCE (h) and
Pd-NPs-GCE (o) [21] [(A) reprinted with permission from American Chemical Society, (B) Wiley-VCH Verlag GmbH & Co. KGaA, reproduced
with permission, and (C) reprinted with permission from Elsevier].

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Trends in Analytical Chemistry, Vol. 30, No. 11, 2011 Trends

charges or selectively bind to active regions on the bio- trode or chitosan-modified electrode was related to the
molecule surface. presence of Au-NPs and their catalytic behavior.
Enzymes usually lack direct electrical communication Although enzymatic sensors are more suitable for
with the electrode substrate due to their active centers environmental monitoring, for rapid and simple mea-
being surrounded by a protein shell. Electron transfer surements in the field, their application is still limited, as
between the electrodes and the active centers is blocked. they need the substrate to activate or to maintain en-
The conductivity of NPs enhances the rate of direct zyme activity over a lengthy storage time [25,30].
electron transfer between the active site of the enzymes
and electrodes acting as electrical wires. Among different
types of NPs, Au-NPs, Pt-NPs, and Ag-NPs have shown 3.3. Non-enzymatic sensors
biocompatibility with enzymes (e.g., in several recent The sensing ability of NPs in non-enzymatic sensors is
publications, it was shown that Au-NPs could be used as directly related to their catalytic property. For example,
a conduit for electrons from enzyme redox reactions using a seed-mediated growth technique, Cui et al.
[24]). Due to their biocompatibility, Au-NPs are consid- deposited Au-NPs (mean size 4 nm) on a glassy carbon
ered an excellent option for replacing potentially harmful (GC) electrode [31], which showed excellent catalytic
mediators in the construction of biosensors [25]. The activity towards the oxidation of nitrite in a real waste-
electrode-surface environment and the amount of NPs water sample without any major interference.
deposited are also crucial in design of enzyme-based However, the catalytic properties of NPs depend on the
electrochemical sensors. protecting groups or the presence of additives (e.g.,
Among different enzymes or proteins commercially cysteine or tannic acid). Controlling NP size, it is possible
available, acetyl cholinesterase (AChE) and tyrosinase to change the catalytic activity of NPs so that it becomes
(TY) and, in a few cases, hemoglobin protein (Hb) have sensitive to different oxidation states of one species. For
been used in construction of enzyme-based sensors for example, controlling the size of Au-NPs allows Cr(VI) to
environmental monitoring. be measured electrochemically in the presence of excess
The application of AChE-nanomaterial-modified elec- of Cr(III), offering benefits over the commonly-used
trodes for analysis of pesticides was recently reviewed by diethylenetriamine-pentaacetic-acid (DTPA) method
Periasamy et al. [26]. In brief, in most AChE-based [32]. The stability and activity of this electrode depended
sensors, organophosphorous (OP)-pesticide detection is on the size and the density of the NPs. Larger NPs were
mainly based on the irreversible inhibition of AChE shown to cause not only a negative shift in peak po-
activity by OP pesticides. The degree of inhibition is tential and lower peak current but also deterioration in
calculated by comparison of the residual activity of the the stability due to the blocking electron transfer be-
enzyme with the initial activity. tween solution species and electrode. This sensor was
TY-NP-based electrodes are usually used for detection applied to measure Cr(VI) in tap water, stream water,
of phenolic compounds. The mechanism is based on the and sea water [32].
oxidation of phenolic compounds (e.g., herbicide atra- NPs provide a larger surface area for detection of
zine) by tyrosinase to catechol and further to quinone analytes, leading to electrochemical sensors with lower
[27]. LODs. For example, Au is known to be the most appro-
Hemoglobin (Hb) is known for its catalytic activity priate material to measure arsenic but the analysis of
towards the reduction of nitrite. However, it is difficult arsenic by the anodic stripping voltammetry (ASV)
for Hb in solution to exchange electrons directly with method is limited by the formation of a monolayer of As0
bare solid electrodes, as its electroactive center (heme) is deposition due to non-conductive property of the As-Au
buried in its electrochemically-insulated peptide back- compound. Au-NPs with large surface area are used to
bone and, furthermore, its adsorption on the electrode overcome this limitation in many studies, but their per-
surface deteriorates its bioactivity and results in dena- formance depends on their size, shape and distribution
turation. NPs may provide a mediator to facilitate elec- during the nucleation process, which is followed by
tron exchange for Hb [28]. particle growth [17,33]. Another example is the detec-
A more uniform film can be obtained when NPs are tion of lead. Lead in acidic media shows UPD on Au
deposited in a polymer, for example, Au-NPs were co- electrodes but the maximum response of this process is
deposited with a biocompatible polymer (chitosan) on limited by the electrode area, so the use of Au-NPs with
the electrode surface to obtain more uniform films [29]. large surface area can solve this problem [34]. Studies
The AChE was then immobilized on this electrode to have also shown that increasing the surface roughness
provide an amperometric sensor to measure different OP of a platinum electrode via platinization provides more
pesticides (e.g., malathion, pralidoxime iodide, and active sites for catalyzing the oxidation of CO to CO2,
monocrotopos). The peak current for oxidation of thi- leading to increase in sensitivity of this sensor [35]. NPs
ocholine (hydrolysis product of AChE) increased. A can also be used in preparing paste electrodes. In this
negative shift in peak potential compared to bare elec- type of electrode, the presence of NPs increases the

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Trends Trends in Analytical Chemistry, Vol. 30, No. 11, 2011

surface area of the paste and diminishes the Ohmic tions to give a uniform dispersion of Ag-NPs on CNTs
resistance of the paste [36]. [37].
The small size of NPs and their resulting large sur-
face area can lead to NP-NP aggregation when pre-
paring the sensor. To avoid this, the surface of NPs 4. Sensitivity and selectivity
can be functionalized with thiol groups or other self-
assembled monolayers (SAMs) containing amino or 4.1. Sensors based on metal nanoparticles
carboxylic acid groups. These functional groups Metal NPs (e.g., Au, Pt, Pd and Ag) show catalytic
introduce new functions in sensor design. In the case activity when they are incorporated into electrochemical
of Au-NPs (mean size 5 nm), SAMs stabilize the par- sensors. For example, an electrochemical sensor based
ticles by preventing aggregation. They can also provide on Au-NPs (mean diameter 46 nm) embedded in 3-
an insulating medium between metallic gold cores aminopropyl)triethoxysilane (APS)-derived silicate sol
[18]. In the case of highly monodispersed benzyl gel three-dimensional network (APSAu-NPs) was pre-
mercaptane-stabilized Ag-NP-modified carbon nano- pared for simultaneous detection of N2H4, SO32 and
tubes (CNTs) on a GC electrode, the phenyl rings of NO2 (see Fig. 3). The electro-oxidation peaks appeared
benzyl mercaptane attach to the side wall of CNTs and at 0.05 V, 0.20 V, and 0.55 V vs. Ag/AgCl for N2H4,
the free thiol groups at the end of the molecules SO32 and NO2 in pH 7.2 at the APSAu-NP-modified
interact with Ag-NPs to form strong S-Ag bonds. The GC electrode with a large decrease in the overpotentials
benzyl mercaptane prevents Ag-NPs from aggregation to the extent of 750 mV, 600 mV and 250 mV, respec-
and promotes interaction with CNTs via pp interac- tively [38]. Ion-exchange membranes [e.g., Nafion (a

Figure 3. Cyclic voltammograms (scan rate 50 mV/s) at (a) GCE, (b) GCE/APS, (c) GCE/APS-Au-NPs for (A) 250 lM N2H4, (B) SO32 and
(C) nitrite (D) (scan rate 20 mV/s) for a mixture containing 250 lM of N2H4, SO32 -and nitrite in 0.1 M PBS pH = 7.2 [38] (reprinted with
permission from Elsevier).

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Trends in Analytical Chemistry, Vol. 30, No. 11, 2011 Trends

negatively charged membrane)] can be used beneficially electrode surfaces with bioconjugates of Ag-NPs (mean
in the sensor design. A screen-printed electrode was diameter 11 nm) and hemoglobin for determination of
modified with a paste of Bi-NPs (mean diameter 50 nm) nitric oxide [43]. The UV-Vis absorption spectrum con-
and Nafion as a binder to help the NPs to adhere to the firmed a similar Soret band (405.6 nm) for both Hb with
electrode surface. Well-defined and highly-reproducible and without Ag-NPs, consistent with Ag-NPs preserving
electrochemical responses were obtained for detection of the natural conformation of Hb. The increased rate of
Zn(II), Cd(II) and Pb(II) using ASV [39]. The presence of electron transfer confirmed the electron-transfer process
Nafion causes the peak potentials to shift to more neg- between protein and electrode was effective. Both elec-
ative values due to the cation-exchange behavior of the trochemical reactivity of the protein and its detection
Nafion coating, which favors an oxidized state of the sensitivity toward NO were enhanced in presence of Ag-
metal ions. Coating the composite electrode with a Naf- NPs.
ion membrane also helped in avoiding anionic interfer- NPs fixed in an organic matrix have proved to be very
ence in the sample (NO3, SO42, CO32). useful in construction of electrochemical sensors. The
A poly (L -lactide)-stabilized Au-NP-modified (PLA-Au NPs represent the electronic conductivity while the or-
film) electrode has been used for the indirect detection of ganic matrix has the selective binding sites for selective
sulfide by measuring the inhibited oxidation current of adsorption of analyte molecules. An interesting part of
As(III) in acidic medium [40]. A substantial decrease in this approach is the ability to control the sensor prop-
oxidation peak current for As(III) in the presence of erties by molecular design. The charge transport in such
sulfide was obtained and it was related to the formation NP assemblies sensitively depends on the particle size,
of As2S3 compound. the interparticle spacing and the chemical composition
Using this approach with differential pulse stripping (i.e. the electronic structure of the stabilizing or inter-
voltammetry (DPSV), the amount of sulfide in hot spring connecting ligands). Thus, selective absorption of ana-
water and acid rain was determined with an LOD of lytes to the organic matrix among the NPs can be
0.04 lM. The following mechanism was suggested for utilized to affect the electrical transport in such hybrid
this reaction based on arsenite existing in the form of systems (e.g., Wohltjen and Snow developed a colloidal
H3AsO3 in acidic media (see Fig. 4). metal-insulator-metal ensemble chemiresistor sensor
based on a monolayer of octanethiol-stabilized Au-NPs
Na2 S 2HCl ! H 2 S 2NaCl1 transducer film for ppm detection of toluene and tetra-
2H 3 AsO3 3H 2 S ! As2 S3 6H 2 O2 chloroethylene [44]).
Pt-NPs have been used in construction of electro-
The detection of cyanide and thiocyanide anions in chemical sensors for detecting CO, CO2, NO2, NO,
wastewater and industrial samples was reported at formaldehyde, methanol, naphthols, phenol, mercury
Ag-NP-modified electrodes based on the complexation and As(III). Pt-NPs can oxidize CO to CO2 in the presence
reaction of Ag+ with these anions. The electron-transfer of interferences (e.g., Cl2, SO2, H2S, NO2 and NO) and
reaction in these processes is controlled by the adsorp- have been employed for applications in environmental
tion of CN or SCN. For example, Taheri et al. devel- pollution monitoring [45]. The adsorption of CO was
oped a cyanide sensor based on mercapto- shown to be purely chemical and irreversible at Pt-NP
propyltrimethoxy-silane (MPS)-stabilized Ag-NPs (mean diameter 18 nm)-modified electrodes. In this case,
embedded in 3D sol-gel matrix on a gold electrode [41]. CO oxidation occurred through the reaction of adsorbed
MPS acts here as a capping agent. The cathodic current CO with Pt-OH to form CO2 following the reaction
for an Ag-NP-modified electrode decreases in the pres- pathway indicated by following equation:
ence of cyanide ions because of the formation of the
CO H 2 O ! CO2 2H 2e 3
Ag+CN complex. The peak current decreases due to
the blockage of the electrode surface by this complex so Photinon et al. showed that the catalytic activity of Pt-
that less surface area of NPs is available. This electrode NPs toward oxidation of CO and the sensor response
was successfully applied for determination of cyanide in depend on the crystallographic orientation of platinum
industrial samples. In another study, an oleate-stabilized deposits [46]. It is known that CO2 adsorbs preferentially
Ag-NP (mean diameter 22 nm)-modified GC electrode on the hydrogen-treated Pt surfaces (Pt-H), so detection
was prepared as an amperometric sensor for thiocya- of Pt-HCOO in acidic media on Pt surfaces is a method to
nate. In the presence of SCN, a new oxidation peak quantify CO2 in a gaseous test environment. The anodic
appeared, due to the formation of the Ag+SCN com- adsorptive stripping of CO2 at high and low concentra-
plex and the anodic peak current for Ag-NPs decreased tions shows the inverse relationship between Pt-H and
due to the electro-reductive activity of Ag-NPs [42]. Pt-HCOO, as depicted in Fig. 5.
Ag-NPs with relatively high specific surface area can Electrochemical measurement of As is usually
integrate proteins and help in orientation of adsorbed accompanied by interference from Cu. However, Pt-NP-
proteins. Gan et al. modified the pyrolytic graphite- modified electrodes was shown to be less sensitive to Cu,

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Trends Trends in Analytical Chemistry, Vol. 30, No. 11, 2011

Figure 4. Indirect detection of sulfide by measuring the inhibited oxidation current of As(III) in acidic medium at poly (L -lactide) stabilized Au-
NP-modified (PLA-Au film) electrode [40] (with kind permission from Elsevier).

especially for low concentrations of As (less than and the presence of Fe(III) was shown to be an important
100 ppm) [47]. The mechanism suggested for this factor for the kinetics of NP growth. This sensor
detection strategy involved formation of PtOH on the showed good response for detection of nitrite in the
electrode surface followed by binding As(OH)3 and presence of interferences (e.g., 500-fold Na+, K+, Mg2+,
electron transfer. Ni2+, Cu2+, Cl, NO3, SO42, CO32; 200-fold H2O2;
The characteristics of mixed-metal NPs, especially 100-fold SO32, S2O32, L -glutamic acid; and, 50-fold
their catalytic property, are quite distinct from those of dopamine, uric acid, ascorbic acid, glucose, D -fructose,
pure-metal NPs. Also, their nano-composite structures sucrose, oxalic acid, citric acid, D -galactose and malic
are of interest. Very few studies have addressed the co- acid). An LOD of 0.47 lM was obtained for this electrode
deposition of Pt-NPs and a transition-metal oxide for [48].
improving efficient catalysis. For example, co-deposition In another study, the co-deposition of Pt and Pd-NPs
of Pt-NPs (mean diameter 6 nm) and Fe(III) on a GC on a Nafion-modified GC electrode was reported by Zhou
electrode resulted in a sensor with good catalytic ability et al. [49]. This sensor showed remarkable electrocata-
toward the oxidation of nitrite. The Pt-NPs were caged lytic activity towards oxidation of formaldehyde in
by the Fe(III) network formed by the FeOFe linkages, aqueous solution of H2SO4 with a broad linear range and

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Trends in Analytical Chemistry, Vol. 30, No. 11, 2011 Trends

Figure 5. Sketches for anodic stripping of CO2 at low and high concentrations showing the inverse relationship between Pt-H and Pt-HCOO
[46]. E1 is the potential where CO2 adsorbs on the Pt-H surface (0.3 V vs. RHE). E2 is the potential where the non-reacted Pt-H is oxidized from
the electrode (0.5 V vs. RHE). E3 is the potential where Pt-HCOO is oxidized (0.75 V vs. RHE).

a low LOD. The PtPd alloy has a synergistic effect to 4.2. Sensors based on metal-oxide nanoparticles
minimize the poisoning of the electrode surface by Metal oxides provide robust building blocks in nano-
reaction intermediates, particularly CO. structures and offer functionality from electrically con-
Specific interactions between the analyte species and ducting to insulating and from highly catalytic to inert.
the organic-shell functional groups on NPs could en- Application of metal oxides in sensors, although less pre-
hance sensitivity and increase the selectivity of the valent, is therefore very promising [52]. Zirconia (ZrO2)-
sensor. For example, a GC electrode modified with NPs are selective sorbents in electrochemical sensors for
Au-NPs capped with 11-mercaptoundecanoic acid units detection of OP pesticides and nerve agents. Zirconia has a
was used for detection of Cu2+ ions and a sensitivity strong affinity towards phosphorous groups, so nitroaro-
below 1 ppb with improved selectivity in the presence of matic OPs strongly bind to the ZrO2-NP surfaces [53]. The
Fe3+ and Zn2+ ions was reported [50]. Multilayers of ZrO2-NP also provide a large surface area and increase the
conductive NPs gave rise to a large porous surface-area interaction with OP compounds (e.g., methyl parathion,
electrode, where the local microenvironment of the paraoxone and fentrothion).
metallic NPs was controlled by the cross-linking ele- Iron-oxide NPs have been used as the immobilizing
ments. Jena et al. modified an Au-electrode surface with matrix for applications in biosensing due to their good
a thiol-functionalized sol-gel derived from 3D silicate biocompatibility, low toxicity, high electron-transfer
networks via 3-(mercaptopropyl)-trimethoxy-silane capability, and high adsorption ability. Iron-oxide NPs
(MPTS) and soaked the electrode in citrate stabilized Au- provide a favorable environment for immobilization of
NPs (mean size 56 nm) solution for self assembly of Au- many biological molecules. For example, Kaushik et al.
NPs on the thiol groups. A random distribution of immobilized single-standard calf-thymus DNA onto
Au-NPs through the network with a size distribution of chitosan-Fe3O4 hybrid nanobiocomposite film (Fe3O4-
70100 nm was obtained. It was shown that the overlap NPs, mean diameter 22 nm) and deposited it onto an
between the diffusion layers at individual Au-NPs pro- ITO substrate for detection of pyrethroids (insecticides)
duced a diffusion layer linear to the geometrical surface (e.g., cypermethirn (CM) and permethrin (PM) [54]). The
area of the electrode. This electrode showed a good presence of Fe3O4-NPs on the ITO electrode surface in-
performance for simultaneous detection of As(III), Hg(II) creased the electroactive surface area and also promoted
and Cu(II) (5 ppb) in a real sample from an arsenic- electron transfer due to the uniform dispersion
contaminated area in West Bengal [51]. throughout the chitosan network on the electrode.

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Trends Trends in Analytical Chemistry, Vol. 30, No. 11, 2011

Metal-oxide semiconductors (e.g., WO3, TiO2, ZnO and 5. Outlook and conclusion
SnO2) are widely used in gas sensors, having high
detection ability and stability. However, the application NPs have proved to be successful in the preparation of
of NPs as gas-sensing elements is usually limited to improved electrochemical sensors. However, developing
chemiresistors, which have been reviewed by Franke new types of NPs for electrochemical-sensor applications
et al. [55]. The electrical resistance of chemiresistors with good stability and selectivity remains a challenge.
changes in the presence of an oxidizing or reducing gas. Compared to NP applications in medicine and bionano-
Many gas sensors operate by detecting changes in the technology, NP applications in electrochemical envi-
electrical properties of a nanostructured sensing-film ronmental monitoring are still underdeveloped. Recent
material in the presence of a test gas. A review by research shows that NPs have considerable potential in
Toohey addresses the influence of electrode material and improving electrochemical-sensor design for the detec-
NP geometry on sensitivity and selectivity of gas sensors tion of a wide range of environmental contaminants.
[56]. The gas-sensing NPs (e.g., ZnO, SnO2, TiO2, and Most of the research in this area has been devoted to the
WO3) can be deposited on a gold or platinum electrode as development of the new methodologies for fabricating
a substrate. These sensors operate through transference new sensors rather than optimizing their performance
in the equilibrium of the surface-oxygen reaction by the (sensitivity or selectivity). Furthermore, sensors are
presence of the target analyte. A reducing gas increases rarely tested with real or industrial samples (e.g.,
the conductivity of an n-type semiconductor and de- wastewater), which show considerable analytical com-
creases the conductivity of a p-type semiconductor, and plexity where NP sensors may offer further advantages.
an oxidizing gas behaves vice versa. The use of NP metal It is important to understand NP chemistry, reactivity
oxides increases the sensitivity of the sensor when the and possible mechanisms involved in their interaction
surface-oxygen chemisorption reaction determines the with the analyte. More work will be required to exploit
sensor response [57]. the recent availability of new nano-building blocks and
Mixed metal-oxide-semiconductor NPs enhance the better surface science tools for the structural and
performance of the electrochemical sensors. For exam- mechanical analysis of processes at NP surfaces. Finally,
ple, Yuasa et al. loaded PdO-NPs on SnO2-NPs as a a wide range of entirely new sensor materials based on
highly sensitive CO gas sensor [58]. They showed that nano-composites is now possible (e.g., mixed metal
the NP size of PdO on SnO2NPs has a significant effect on metal oxide) and interfacial processes at new types of
gas-sensing properties. By reducing the size of the PdO- NPNP interfaces are accessible. The application of these
NPs, the number of PdO-NPs in contact with SnO2-NPs materials in environmental sensing should enable more
increases, so the electrical resistance increases by an advanced electrochemical-sensor systems to be devised
order of magnitude. This is because PdO acts as a strong in the near future.
acceptor of electrons and removes electrons from the
oxide. However, when PdO is reduced to Pd by the
reducing gases, the resistance decreases by back-electron Acknowledgements
transfer from Pd to SnO2. The difference in the electrical L.R. gratefully acknowledges helpful discussions with
resistance of SnO2 induced by a change in the oxidized Dr. Mohammad Khazaei (Institute for Materials
and reduced states of Pd is often large, giving rise to a Research, Tohoku University, Japan) and the financial
large increase in response to the reducing gases. support from EPSRC, European Union and TEKES.
In another study, WO3-NPs doped with cerium as
electrode material was developed for monitoring of
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