Indian Journal of Chemistry

Vol. 51A, Jan-Feb 2012, pp. 205-225

Surface modification in electroanalysis: Past, present and future

Rajendra N Goyal* & Sunita Bishnoi
Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee 247 667, India
Email: rngcyfcy@iitr.ernet.in
Received 27 October 2011

This review discusses the electrochemical sensors and biosensors based on carbon nanotubes, fullerenes, metal
nanoparticles and ionic liquid/composite modified electrodes. Subsequently, recent developments and major strategies for
enhancing sensing performance, the challenges and prospects of further developments in the future are debated. Besides a
brief exposition of the properties of ionic liquids and their general applications based on these properties, this review focuses
on the application of ionic liquids in electroanalytical sensors. Emphasis is given to direct electron-transfer reaction, origin
of electrocatalysis effect of nanomaterials and use of these sensors to determine the level of biomolecules, drugs/doping
agents in human body fluids. This review aims to expand on these aspects by covering the most recent trends and advances
in the utilization of nanomaterials in electroanalytical techniques during the last decade or so.

Keywords: Electrochemistry, Electroanalysis, Modified electrodes, Surface modification, Electrode modification, Sensors,
Biosensors, Nanomaterials, Carbon nanotubes, Fullerenes, Ionic liquids

Exploitation of nanomaterials and nanoparticles in Carbon Nanotubes and Fullerenes

electroanalysis is an area of research that is
continually growing. Surface modification of
conventional electrodes for enhanced current response
is very important in developing a stable and highly
target specific interface. Sensitivity and selectivity are
the crucial issues for the development of sensors for
detecting biologically important molecules. The aim
of this article is to provide an overview of the recent
works in this field including advantages and
disadvantages of surface modification by carbon
nanotubes, fullerenes and metal particles. Herein we
have focused on the benefits of electrode surface
modification as shown by sensor performance in
terms of voltammetric response to the target
compounds using nanoparticles, nanomaterials,
combination of nanoparticles with nanotubes and
ionic liquid with carbon paste. This review does not
cover all aspects of nanomaterials in electrochemistry
and is restricted to electrochemical sensors based on
the traditional electrochemical method, voltammetry
and does not cover other methods like potentiometry,
impedance spectroscopy and piezoelectricity. In
addition to the origin of electrocatalytic activities of
different types of nanomaterials and their fundamental
electrochemical knowledge, this article also attempts
to focus on pharmaceutical and biomedical
applications of various nanomaterials/nanaoparticles-
based electrochemical sensors.
The subtle electronic properties of carbon
nanotubes suggest that they have the ability to
promote electron transfer reactions when used as an
electrode in electrochemical reactions. This provides a
new application in the electrode surface modification
for designing new electrochemical sensors and novel
electrocatalytic materials1. As a new type of
carbonaceous material, carbon nanotubes (CNTs)
possess some unique properties that are very different
from the conventional scaled materials. Such
properties include well-defined tubular structure of
nanosizes, functional surfaces, modifiable ends and
sidewalls, excellent chemical stability, strong
electrocatalytic activity and excellent
2
biocompatibility . The three-dimensional special
architecture of the CNTs can lead to a high loading of
electrocatalysis or biomaterial onto the solid substrate
and thus can enhance the efficiency for
(bio)electrocatalysis. As tubular nanomaterials, the
key advantages of CNTs are their small diameter and
large length-to-diameter ratio that allows them to be
used as molecular wires for facilitating electron
transfer between biomolecules and electrodes with
ultra-sensitivity. These special properties envisage
promising applications in electroanalytical chemistry
and make CNTs ideal candidates for constructing
sensors with high performances. Both single wall
carbon nanotubes (SWNTs) and multiwall carbon
206 INDIAN J CHEM, SEC A, JAN-FEB 2012
nanotubes (MWNTs) have been widely used in
biosensing3,4.
Peng et al.5 suggested that the intrinsic electronic
properties of carbon nanotubes remain unaffected
even when they are in direct contact with water by an
ab initio study of water adsorbed on single walled
carbon nanotubes which showed purely repulsive
interaction without any charge transfer5. This study
revealed new avenues for application of carbon
nanotubes modified sensors in aqueous medium. The
modification of electrodes with CNTs has been
observed to apparently improve the response of
substrates from small H2O2 molecules to huge redox
proteins. The electron transfer and the direct
electrochemistry of redox proteins at CNTs based
electrochemical sensors are well reported6,7. Excellent
improvement in the electrochemical behavior of
biologically important compounds such as dopamine
and ascorbic acid8,9, quercetin and rutine10,
tryptophan11, tyrosine12, procaine13 and metformine14
has been demonstrated at CNTs modified electrodes.
CNTs modified electrodes have also been utilized to
determine hemoglobin in bovine blood15. Multi-
walled carbon nanotubes modified carbon paste
electrode (MWNT/CPE) has been used to study the
electrochemical behavior of Bergenin16. The modified
electrode showed excellent electrocatalytic activity in
lowering the anodic overpotential and remarkable
enhancement in anodic peak current of bergenin as
compared to the electrochemical performance
obtained at CPE. Conventional electrodes are found
not suitable for the determination of catecholamines,
viz., epinephrine (EP) and norepinephrine (NE) due to
interference from ascorbic acid (AA) and uric acid
(UA), which co-exist in a real sample at 100 times
higher concentration than EP and NE. These
compounds can be easily oxidized at a similar
potential of EP and NE and thus always interfere with
EP and NE detection. Goyal et al.17,18 have developed
a MWNT modified pyrolytic graphite electrode which
can be used to simultaneously monitor different
biomolecules. Ascorbic acid, dopamine,
norepinephrine and uric acid show oxidation peaks at
−50, 80, 204 and 260 mV respectively and do not
interfere with the oxidation of epinephrine,
confirming thereby that this voltammetric sensor is
specific for the oxidation of epinephrine at 150 mV.
The proposed sensor has also been utilized for the
determination of of epinephrine in human urine and
plasma samples of smokers and non-smokers and it is
found that the level of epinephrine in smokers is much
higher than that in non-smokers. Hydrogen peroxide
(H2O2) is a product of several biological enzyme-
catalyzed reactions. The detection of H2O2 plays an
important role in food industry, environmental
protection, and in medical diagnostics. For the
sensitive detection of H2O2, Tkac and Ruzgas19 have
used an electrode modified with SWNT, the
sensitivity of which was highly dependent on the
dispersing agent in the organic solvents and charging
status of polymers (e.g. Nafion and chitosan). It is
found that the dispersion of both polymers is highly
stable but the SWNT in the chitosan dispersion
showed higher sensitivity for H2O2 as compared to
that in Nafion. The single walled carbon nanotube
modified gold detector for microchip capillary
electrophoresis (CE) has been constructed and
successfully used for the detection of p-aminophenol,
o-aminophenol, dopamine and catechol20. SWNT
modified glucose biosensors exhibited a wider
dynamic range and greater sensitivity in glucose
determination21. Rutin is a flavonoid glycoside that
has a wide range of physiological activities such as
antiinflammatory, antitumor and antibacterial. CNT
modified electrodes have been successfully used for
the determination of rutin. A gold electrode modified
with SWNT was fabricated by Zeng et al.22 to
investigate the voltammetric behavior of rutin. The
anodic (Epa) and cathodic peak current ratio of 1,
indicates that the electrode reaction is almost
reversible. The method has been applied for the
determination of rutin in medicinal samples. Based on
the interaction of hemoglobin with rutin, this
procedure has also been used for the indirect
determination of hemoglobin. A nanocomposite of
poly- Nile blue with SWNT modified glassy carbon
demonstrated the ability to electrocatalyze the
oxidation of NADPH at a very low potential
(– 80 mV versus SCE) with a substantial decrease in
the overpotential by more than 700 mV as compared
with the bare GCE23.
Our laboratory is also actively studying the
electrochemical determination of a variety of
biomolecules and drugs using CNT and fullerene
modified electrodes24-38. Pyrolytic graphite electrode
(PGE) has been explored as a substrate for the surface
modification. The two planes of PGE, namely, edge
plane (EPPGE) and basal plane (BPPGE) were
modified with single-wall carbon nanotubes (SWNT)
or with multiwall carbon nanotubes (MWNT) and
 GOYAL & BISHNOI: SURFACE MODIFICATION IN ELECTROANALYSIS
used as sensors to determine a variety of steroids and
drugs. A simple and highly sensitive sensor based on
EPPGE coated with SWNT has been proposed24
for diclofenac determination in nanomolar
concentrations. The modified electrode showed
excellent catalytic activity, presenting much higher
peak currents than those measured on a bare EPPGE.
The purity of SWNT also affected the peak potential
and peak current as shown in Table 1. Thus, it is
concluded that embedded metals in MWNT play a
significant role in electrocatalysis. The detection limit
at peak I is almost ten times lower than that observed
at bare PGE. The electrode showed good sensitivity,
selectivity, reproducibility and high stability with
remarkable electrocatalytic properties.
The modification of pyrolytic graphite electrode
using carbon nanotubes has been found to offer a
marked decrease in the peak potential, high
sensitivity, low detection limit and stable
voltammetric sensing for amlodipine. A detailed
comparison of MWNT and SWNT modified EPPGE
towards the oxidation of amlodipine indicates the
enhanced performance of SWNT as a novel electrode
surface modifier in comparison to MWNT25. The
simultaneous determination of prednisolone and
prednisone in human body fluids and pharmaceutical
preparations has been proposed26 by using square
wave voltammetry (SWV) in phosphate buffer
medium of pH 7.2. The SWNT modified electrode
exhibited good electrocatalytic properties towards
prednisone and prednisolone reduction with a peak
potential separation of 100 mV. The results of the
quantitative estimation of prednisone and
prednisolone in biological fluids were also compared
with estimation by HPLC; the results were in good
agreement. A sensitive voltammetric method has been
described for the determination of betamethasone
sodium phosphate (BSP) using EPPGE modified
with SWNT-cetyltrimethyl ammonium bromide
nanocomposite film27. The voltammetric response of
betamethasone enhanced effectively using cationic
surfactant cetyltrimethylammonium bromide (CTAB)
as electrode surface modifier. The nanotubes-
surfactant modified EPPGE showed great
improvement in peak current and shifted the reduction
potential towards less negative potential. The role of
cetyltrimethylammonium bromide on electrocatalytic
property is discussed. The analytical utility of the
developed method is demonstrated by the direct assay
of betamethasone in urine samples of pregnant
207
Table 1⎯Effect of metallic contents of SWNT on peak potential
and peak current of peak I of 50 nM diclofenac in phosphate
buffer of pH 7.2
Sample Metal content (%) Diclofenac
Fe Co Ni Ep (mV) ip (μA)
Untreated 0.819 0.412 0.207 439 22.1
SWNT
Purified SWNT 0.373 0.023 0.101 481 18.5
Super-purified 0.318 0.013 0.078 525 16.3
SWNT
women. A fast and sensitive voltammetric method has
been proposed28 for the determination of salbutamol
at SWNT/EPPGE in human urine. The developed
method has been successfully applied for the
determination of salbutamol in commercial
preparations and human body fluids. Fast analysis of
salbutamol in human urine makes the proposed
method of great interest for detecting doping at the
site of competitive games. The electrochemistry of
bisoprolol fumarate (BF,) has been investigated by
differential pulse voltammetry by Goyal et al.29 at a
SWNT modified glassy carbon electrode (GCE). The
prepared electrode showed an excellent
electrocatalytic activity towards the oxidation of BF
leading to a marked improvement in sensitivity as
compared to bare GCE, where electrochemical
activity for the analyte cannot be observed. A novel
sensing system for monitoring cases of abuse of
betamethasone doping is developed31 using
SWNT/EPPGE and has excellent analytical
characteristics such as lower detection limit, high
sensitivity, satisfactory recovery and selectivity along
with good reproducibility. The method fully satisfies
the requirement of World Anti Doping Agency
(WADA); the limit of detection (LOD) being well
below the minimum required performance limit
(MRPL) of 30 ng/mL for the corticosteroid under
investigation. Therefore, proposed method can be
successfully applied as a wonderful analytical tool in
clinical analysis and anti doping tests for the detection
of illicit administration of betamethasone by athletes.
The advantage of this method is that some common
metabolites like ascorbic acid, uric acid, albumin and
hypoxanthine do not interfere as the determination is
based on reduction. A comparison of the results
observed with this method and those with HPLC
clearly shows that both methods are essentially
similar.
The electrochemical investigation of two corticoid
isomers, viz., testosterone and epitestosterone has
208 INDIAN J CHEM, SEC A, JAN-FEB 2012
been carried out at bare and SWNT modified
EPPGE32. Square wave voltammetry has been used
for the simultaneous determination of isomeric
steroids. This novel method has been successfully
applied for the analysis of testosterone (T) and
epitestosterone (E) in human urine samples of normal
male as well as in patients being treated with
testosterone. The studies clearly revealed that in
control urine samples, the ratio of T/E was in the
range 1.04–1.42, whereas in the patients treated with
testosterone the ratio increased to 5.57 – 5.74. Thus,
the ratio increased nearly five times with a single dose
of testosterone. Hence, it is believed that the
developed method can be easily used for
determination of testosterone doping by athletes. A
comparison of the present method with HPLC
indicates that the method is sensitive and the results
are comparable. The voltammetric oxidation of
paracetamol on SWNT modified EPPGE has also
been explored by using square wave voltammetry33.
Cyclic and square wave voltammetry studies indicate
the oxidation of paracetamol at the electrode surface
through a two-electron reversible step and controlled
by adsorption. Besides semi-infinite planar diffusion,
the role of thin layer diffusion at nanotube modified
electrodes is also suggested. The sensitivity at SWNT
modified EPPGE is ~2 times more than that at
MWNT modified EPPGE. The interfering effect of
physiologically common interferents on the current
response of paracetamol has also been reported. The
applicability of the developed method to determine
the drug in human urine samples obtained after 4 h of
administration of paracetamol has also been
illustrated. The simultaneous determination of
adenosine and inosine has been carried out by Goyal
et al.34 at SWNT modified PGE using square wave
voltammetry. The modified electrode exhibited
remarkable electrocatalytic properties towards
adenosine and inosine The proposed method was also
used to estimate these compounds in µM range in
human blood plasma and urine samples and the
method was validated using HPLC. The use of such
modified electrodes for the determination of purine
derivatives has also been explored35. A simple and
sensitive method based on SWV at SWNT modified
EPPGE is proposed for the simultaneous
determination of adenine and adenosine-5-
monophosphate (5-AMP). The modified electrode
was found to exhibit remarkable electrocatalytic
properties towards adenine and 5-AMP oxidation. The
effect of pH revealed that the oxidation of adenine
and 5-AMP at SWNT modified EPPGE involved an
equal number of electrons and protons. The modified
electrode exhibited high stability and reproducibility.
Purine nucleoside, viz., 2,3-dideoxyadenosine has
also been determined at PGE using voltammetric,
coulometric, spectral studies and product analysis The
studies indicate that the oxidation occurs in an EC
reaction (electrochemical followed by chemical)
involving 6e, 6H+ process at pH 7.2 to give allantoin,
C–C dimer and dideoxyribose as the major products
and a C–O–O–C linked dimer as a minor product.
Tentative mechanisms for the formation of the
products have also been suggested36. A comparison of
peak potential value of 2,3-dideoxyadenosine with
adenosine and 2-deoxyadensoine indicates that the
difference is insignificant which has further been
supported by the calculations of difference of energies
of lowest unoccupied and highest occupied molecular
orbitals.
Since reduction has no or very little interference
from the common metabolites present in human blood
or urine, an electrochemical protocol based on
reduction has been developed to determine
methylprednisolone using SWNT modified EPPGE.
To obtain good sensitivity, instrumental variables
were studied using SWV. The voltammetric results
indicate that SWNT modified EPPGE remarkably
enhances the reduction of methylprednisolone, which
leads to considerable improvement of peak current
with shift of peak potential to less negative values.
The limit of detection was estimated to be 4.5×10−9 M.
The developed method has been used37 for the
determination of methylprednisolone in
pharmaceutical dosages and human blood plasma
samples of patients undergoing treatment with
methylprednisolone. The major metabolites present in
blood plasma did not interfere with the present
investigation as they did not exhibit reduction peak in
the experimental range used. A comparison of results
with HPLC indicates good agreement. In another
attempt, electrochemical sensor employing EPPGE
and BPPGE for the sensitive detection of
hydrocortisone (HC) is delineated for the first time.
HC (cortisol, 11, 17, 2l-trihydroxy-4-pregnene-3,20-
dione) is the main glucocorticosteroid exuded by the
adrenal cortex gland and acts to limit the body's
response to stress. It has been shown that EPPGE
displays a better voltammetric response in comparison
to BPPGE due to its low signal-to-noise ratio,
 GOYAL & BISHNOI: SURFACE MODIFICATION IN ELECTROANALYSIS
increased sensitivity, low detection limit and large
potential window38. The peculiar catalytic activity of
an EPPGE relies on the crystal orientation on its
surface. The high percentage of the edge orientation
results in the high catalytic activity. The edge
orientation on the surface of an EPPGE serves as an
‘‘active site’’ for the reduction of HC. Highly ordered
pyrolytic graphite (HOPG) is used to fabricate the
edge and basal plane electrodes. EPPGE is an
electrode constructed from HOPG where the graphite
layers are perpendicular to the disc surface and are
separated with an interlayer spacing of ~ 3.35 Å.
Surface defects occur in the form of steps exposing
the edges of the graphite layers. Conversely, a
BPPGE is fabricated such that the layers of graphite
lie parallel to the surface. The difference between the
edge and basal orientations may account for the fact
that functional groups are easier to adsorb on the edge
plane. The developed protocol has lower detection
limit (88 × 10−9 M) as compared to the previously
notified at carbon paste electrode modified with
β-cyclodextrin (4.2 × 10−7 M). Triamcinolone, abused by
athletes for doping, has been determined by Goyal et al.39
in human urine samples. The surface modification has
been found to increase the effective surface area of
the electrode to about two times. A comparison of the
voltammetric behavior between SWNT modified PGE
and fullerene–C60-modified EPPGE indicates that the
SWNT modified EPPGE is more sensitive. The
method was applied for the determination of
triamcinolone in several commercially available
Fig.1⎯A comparison of square-wave voltammograms of 10 nM
triamcinolone at pH 7.2 at bare BPPGE (b), bare EPPGE (c),
fullerene modified EPPGE (d) and SWNT modified EPPGE (e).
(a) is the background phosphate buffer solution (pH 7.2) at SWNT
modified EPPGE. [Reproduced from Ref. 39 with permission from
Elsevier, Amsterdam, The Netherlands].
209
pharmaceuticals and real urine samples obtained from
patients undergoing pharmacological treatment with
triamcinolone. A comparison of square wave
voltammograms observed for triamcinolone at
different electrodes is presented in Fig. 1. The studies
indicate that SWNT is a better surface modifier in
comparison to fullerene for the reduction of
triamcinolone, as it accelerates the rate of electron
transfer faster39.
Goyal et al.40 recommended that the
SWNT/EPPGE showed great improvement in
voltammetric response of guanine and 8-hydroxy-
guanine in terms of yield of large peak currents and
lower peak potential as compared to bare EPPGE.
Hence, a simple and reliable method based on
voltammetry is proposed for the determination of
oxidative DNA damage by the simultaneous
determination of guanine and 8-hydroxygunine.
Formic acid was used for DNA hydrolysis since it
does not cause any artifacts. Other purine and
pyrimidine derivatives are also likely to be present in
the matrix. Thymine, adenine and cytosine oxidize at
higher potentials than guanine and 8-hydroxyguanine
and thus do not interfere in the determination.
Figure 2 indicates that at bare EPPGE the oxidation of
guanine and 8-hydroxyguanine occurs with broad
peaks at 640 and 452 mV, respectively. After
modification of electrode, under identical conditions
the peak potential shifted negatively and oxidation
occurred with well-defined peaks at 556 and 360 mV
for guanine and 8-hydroxyguanine, respectively along
with substantial increase in peak current.
Fig. 2⎯Cyclic voltammograms of homogeneous solution of
guanine and 8-hydroxyguanine in PBS of pH 7.2 using (a) bare
edge plane PGE (−·−·−·) and (b) SWNT modified EPPGE ( — ) at
scan rate of 20 mV/s. [Reproduced from Ref. 40 with permission
from Elsevier, Amsterdam, The Netherlands].
210 INDIAN J CHEM, SEC A, JAN-FEB 2012
Origin of electrocatalytic effect of nanotubes
There has been an explosion of research on
modifying electrodes with carbon nanotubes in the
search for the origin of electrocatalytic responses of
nanotubes41-43. It is well documented that such
improvements are due to the unique structure of the
carbon nanotubes, where the presence of edge plane
like-sites/defects lead to heterogeneous charge
transfer44,45. In this regard, Compton’s group41,44
reported an interesting investigation related to the
reason why CNTs present enhanced electrocatalytic
activity and proposed that this activity is due to the
presence of edge-plane like sites located at the end
and the “defects” areas of the tubes. Further, ab initio
calculations demonstrated that the improvement in the
electron transfer is due to the curvature of the tubes
that originate changes in the energy bands close to the
Fermi level46. Pentagonal defects in planar and tubular
structures produce regions with charge density higher
than that observed in the case of hexagonal defects
demonstrating the connection between topological
defects and CNTs electroactivity46. Carbon nanotubes
can be seen as graphene sheets rolled into tubes, with
the cap region more reactive due to a much higher
curve strain than the sidewall. Based on their specific
structures, two distinct surface regions exist in CNT;
the sidewalls and the ends. Opening of the ends of
CNT by physical/chemical treatment produces a
variety of oxygen-containing groups47. Moreover, the
intact CNT sidewalls resemble the basal planes of
pyrolytic graphite and can be regarded as
electrochemically inert to electroactive species. Due
to the presence of defects and oxygen-containing
functional groups, the opened caps have
electrochemical properties similar to those of edge
planes of pyrolytic graphite. Thus, the introduction of
edge-like defect sites and oxygen-containing
functional groups, at both the caps and the sidewalls,
by chemical or physical treatments can significantly
improve the electrochemical properties of CNTs by
changing the electronic structures, surface states and
the wetability of the sidewalls.48 The critical roles of
defect sites and oxygen-containing groups in
enhancing electrochemical performances of CNT-
based electrodes have been proved by several research
works.49,50 The adsorbed acid moieties, during
purification and acid-treatment processes, can also
decrease the electrocatalytic activity of CNTs in
electroanalysis. Pumera and Kolodiazhnyi51 suggested
the use of dc magnetic susceptibility and electron
paramagnetic resonance for screening and quality
control of CNTs before using them in electroanalysis.
Recently, Dai and co-workers52 reported that vertically
aligned nitrogen-doped CNTs can act as a metal-free
electrode with a much better electrocatalytic activity.
The electrocatalytic activity and the electroanalytical
performance at CNTs modified electrodes are
strongly depended on the mode of production of the
CNTs, either by chemical vapour deposition (CVD)
or the arc discharge (ARC) process53. CNTs produced
by CVD appear to be more electrochemically reactive
in their voltammetric study than those produced by
the ARC methodology. The differences in the
electrochemical reactivity are attributed to the smaller
fraction of exposed edge planes at ARC-CNTs and
higher density of edge plane defects at CVD-CNTs.
The electrocatalytic activity of ARC-CNTs can be
increased after pre-anodization. Wang’s group54
illustrated the effect of electrochemical pretreatment
of ARC- and CVD-prepared multi-walled CNTs using
nicotinamide adenine dinucleotide (NAD), ascorbic
acid, hydrazine, and hydrogen peroxide model redox
systems54. The fact that the ARC-CNT displays a
marked improvement in electrochemical reactivity
indicates that the pre-anodization effectively breaks
the end caps of ARC-CNTs to expose new edge
plane-like sites. The influence of metallic impurities
upon the electrochemistry of CNTs has been
discussed by Compton and co-workers55. They
demonstrated that iron-based impurities within carbon
nanotubes are responsible for the electrocatalytic
oxidation of glucose55 and the reduction of hydrogen
peroxide56. Further, it was also established that copper
nanoparticle impurities within CNTs cause the
electrocatalysis of halothane and glucose57. The
residual catalyst nanoparticles that are encapsulated
within the CNT graphene lattice may still be
chemically accessible and could participate in the
redox chemistry of biomarkers through the
intercalation of molecules within the CNT lattice58, as
deep as 12 nm. Differential pulse voltammetric
responses of dopamine at bare PGE and non-treated
as well as acid-treated SWNT modified GCE were
compared by Goyal et al.59 A significant decrease in
peak current of DA at acid-treated SWNT modified
GCE was observed in comparison to raw-SWNT
modified GCE as shown in Fig. 3. A comparison of
peak current and peak potential of DA at purified and
super purified SWNT confirmed that with decrease in
embedded metals, the oxidation becomes difficult.
 GOYAL & BISHNOI: SURFACE MODIFICATION IN ELECTROANALYSIS
Fig. 3⎯Differential pulse voltammograms of 25 μM DA recorded
at pH 7.2 at (i) basal plane pyrolytic graphite electrode, (ii) edge
plane pyrolytic graphite electrode, (iii) super-purified SWNT
modified GCE and (iv) untreated SWNT modified GCE.
[Reproduced from Ref. 59 with permission from Elsevier,
Amsterdam, The Netherlands].
This indicates that metallic impurities present in CNT
are responsible for the enhanced peak current and it is
concluded that 98 % pure SWNT are sufficient for
surface modification and further purification is not
necessary.
An uncontrollable amount of impurities in the CNT
samples is evidently not desirable. However, from a
broader perspective it is possible to direct the
controllable decorating of CNTs with metallic
nanoparticles and use their electrocatalytic properties
in a controllable way for enhancing the performance
of sensors and energy-storage devices.60, 61 Since
carbon nanotubes can be seen as the graphene sheets
rolled into tubes, the electrochemical properties of
carbon nanotubes are comparable to those of the basal
planes of pyrolytic graphite (BPPG). For intact carbon
nanotubes, the defect-free structure makes the whole
tubes possess almost the same properties as that of
BPPG, except that the cap regions may be more
reactive than the sidewall due to the much higher
curve strain. The opening of the ends by
physical/chemical treatments on carbon nanotubes
produces a variety of oxygen-containing groups,
211
Fig. 4⎯Cyclic voltammograms for the reduction of 1 mM
ferricyanide for different carbon electrodes at a scan rate of
100 mV s-1. [Reproduced from Ref. 64 with permission from The
Royal Society of Chemistry, London, UK].
which possess properties similar to those of the edge
planes of PGE62. Due to the simple and well-defined
response at carbon materials, the Fe(CN)63-/Fe(CN)64-
couple has been widely used63 to characterize the
surface properties of all kinds of carbon electrodes
(Fig. 4). Similarly, the electrochemical properties of
carbon nanotube based electrodes are generally
investigated by Fe(CN)63-/Fe(CN)64- as the probe. The
electrochemical behaviour of aligned bundles of
carbon nanotubes with other carbon electrodes of
similar structures was compared by Nugent et al.64
The results indicate that Fe(CN)63-/Fe(CN)64- shows
an ideal redox peak separation of 59 mV at the
aligned multi-walled carbon nanotubes. In
comparison, they reported ΔEp of more than 100 mV
and 700 mV for the basal planes of highly oriented
pyrolytic graphite (HOPG) with and without
electrochemical pretreatments, respectively. In
contrast to the ideal response reported by Nugent et al.64,
Li et al.62 observed much larger ΔEp at single-walled
carbon nanotube modified electrode (ΔEp = 94 mV).
At aligned MWNT with heat pretreatment to remove
impurities like amorphous carbon, ΔEp was observed
as 228 mV. Particularly, for aligned MWNT, the
apparent electron transfer rate was found to correlate
with both the area of the exposed sidewalls (with
graphite basal-plane-like properties) and the density
of graphite edge-plane-like defects.
Fullerenes
An important application of fullerenes is their use
as mediators in electrochemistry for the chemical
modification of electrodes in electrocatalysis.
212 INDIAN J CHEM, SEC A, JAN-FEB 2012
Fullerene (C60 or C70) modified electrodes catalyze the
redox reaction of a variety of compounds due to the
formation of more conducting C60n- species during
partial reduction of C60, which helps electron transfer
at the interface65,66. Fullerene anions (reduced
fullerene) can abstract protons from biomolecules. A
very interesting feature of the partial reduction of
fullerene films in aqueous solutions is the proposed
‘sandwich like’ reduction. Partially reduced fullerene
films have a structure with a polar inner and outer
surface, while the inside is non-polar. The structure
cloaely resembles a biological membrane, raising the
possibility of using fullerene as solid state modifiers
to study the electrochemistry of biomolecules67.
Therefore, fullerene modified electrodes meet the
conditions essential for the analysis of biomolecules,
i.e., excellent reproducibility, high sensitivity, wide
potential range and high stability in biological
samples68. The performance of fullerene –C60–
modified electrodes has been reported to produce
electrocatalytic responses compared to the underlying
electrode for certain target analytes. Jehoul et al.69
demonstrated the formation of C60 film on an
electrode surface by evaporation of fullerene solutions
and suggested the requirement of further studies of its
electrochemistry69. Szucs and co-workers70 explored
gold surfaces for the electrochemical determination of
cytochrome c. Further, the electrochemical response
of cytochrome c was also determined by Csiszar et al.71
using fullerene C60 modified electrodes with optimum
results. Tan, Bond and co-workers72 reported the
electrochemical oxidation of L-cysteine in aqueous
solution using C60-modified glassy carbon electrode.
Goyal et al.73 reported the electrochemical oxidation
of uric acid mediated by C60 supported on glassy
carbon electrodes. The introduction of C60 on the
glassy carbon surface facilitated resolution of the
overlapping voltammetric response of uric acid and
ascorbic acid. Two well-defined voltammetric peaks
with a potential difference of ~150 mV were
observed. Simultaneous voltammetric determination
of adenine and guanine at C60 modified glassy carbon
electrode at physiological pH has been described by
Goyal et al.74. Analytical application of the developed
protocol for determination of (G+C)/(A+T) ratio in
DNA samples has been suggested. Nandrolone (also
known as nortestosterone or 17-hydroxy-19-nor-4-
androsten-3-one) is one of the most abused
androgenic anabolic steroid which occurs naturally in
tiny quantities in the human body. The
electrochemical behaviour of nandrolone has been
investigated at fullerene-C60-modified electrode75. The
modified electrode shows an excellent electrocatalytic
activity towards the oxidation of nandrolone, resulting
in a marked lowering in the peak potential and
considerable improvement of the peak current as
compared to the electrochemical activity at the bare
glassy carbon electrode. This method was successfully
employed for the determination of nandrolone in
human blood serum and urine samples. Simlarly,
adenosine and guanosine have also been studied by the
same group76. This method was not only easy to
perform, but also required less time, financial input and
sample amount than other reported approaches, and
hence, is an attractive alternative to HPLC analysis in
both routine and research laboratories.
Origin of electrocatalytic activity of fullerenes
The unique structure of C60 has a distinct lack of
edge plane like-sites/defects78,79 and consequently the
origin of the reported electrocatalysis is quite
interesting. The work by Compton and co-workers80
has clearly indicated that the origin of the
electrocatalytic response observed at C60 modified
carbon electrodes as reported by Tan, Bond and
co-workers for the electrocatalytic detection of
cysteine72 is unambiguously due to graphite impurities
in C60. More recently, determination of salbutamol81
and dopamine in the presence of ascorbic acid82 have
been reported using C60–modified electrodes. The
authors of these reports suggest that the observed
electrocatalytic activity is due to the partially reduced
conductive C60 film in addition to graphite impurities.
The reduction of C60 films in aqueous media is in fact
the electrochemically reversible reduction of
adventitious C60On, with subsequent rapid loss of
“O2−” in an irreversible chemical step. There is no
evidence that C60 itself is reduced within the potential
window of aqueous electrolytes. In another attempt, in
the case of the target analyte nandrolone, Goyal and
co-workers83 have carefully examined the effect of
metallic impurities in the C60 and found that just like
with CNT, the removal of embedded metals from
fullerene shifts the peak potential of nandrolone to
more positive potentials with decrease in peak current
as shown in Table 2. Thus, the untreated fullerene
modified electrode exhibits enhanced catalytic effect
as compared to the acid purified and super-purified
C60 modified electrodes.
Although, the origin of the electrocatalysis has
always been attributed due to partially reduced
 GOYAL & BISHNOI: SURFACE MODIFICATION IN ELECTROANALYSIS
Table 2⎯Effect of metallic contents of fullerene on peak potential and peak current of nandrolone in phosphate buffer of pH 7.2
Sample Metal content (%)
Fe Cu
Untreated fullerenes 0.416 0.191
Purified fullerenes 0.162 0.164
Super-purified fullerenes 0.099 0.071
conductive C60 film, recent reports have indicated that
this is not the only reason. The presence of graphite
impurities84, metal impurities85 and the pretreatment
employed86 may all be the origin or contribute
significantly to the observed electrocatalysis at
C60–modified electrodes depending on the
experimental parameters, chosen not only during the
electrochemical measurements, but also during the
synthesis of fullerenes. It is likely that other
overlooked parameters may also contribute to the
electrocatalytic effect of C60 modified electrodes and,
thus it is recommended that control experiments
should be performed before electrocatalysis of C60
modified electrodes is claimed. It must also be
realized that it is practically impossible to get 100 %
pure fullerenes without breaking the structure as
embedded metals in the cavities cannot be completely
removed.
Metal Nanoparticles
Metal nanoparticles (NP) have wide applications in
different kinds of electroanalytical methods and can
be used to construct novel and improved sensing
devices, particularly electrochemical sensors and
biosensors. Owing to their small size (in order of
1-100 nm) metal nanoparticles exhibit unique
chemical, physical and electronic properties. They can
absorb biomolecules strongly and play an important
role in the modification of electrodes to improve their
electrocatalytic activities. Metal nanoparticles
increase electrochemical activities as they exhibit
higher catalytic efficiency per gram than the bulk
materials, good performance, enhancement of mass
transport and good biocompatibility. Bioactivity of
biomolecules is retained on the surface of
nanoparticles due to their biocompatibility. Metal
nanomaterials enhance the performance of the
biosensors by enlarging the effective surface area87.
Large surface area of deposited metal nanoparticles
permits improvement of analytical performance in
terms of low detection limit and short deposition time.
Transition metal nanomaterials possess high catalytic
activity and facilitate electron transfer for many
213
Nandrolone
Co Ni Ep (mV) ip (μA)
0.007 0.392 456 11.7
0.001 0.263 492 7.25
0.001 0.086 548 5.43
electrochemical reactions. A wide variety of metallic
nanoparticles have been studied to assess the
applications of these materials in electroanalysis.
Biosensors incorporating metal nanomaterials,
including platinum black88, copper89, silver90
palladium91 and gold92 have exhibited good
biocompatibility and enhanced performance.
Nanoparticles of bismuth and iridium have also been
synthesized recently.
Campbell et al.93 studied H2O2 reduction at a silver
nanoparticles (AgNPs) on BPPGE, and have shown
that the voltammetric trace for H2O2 reduction varies
with both nanoparticles size and the extent of surface
coverage. A decrease in nanoparticles size causes a
negative shift in the peak potential, whereas
increasing coverage causes a positive shift.
Additionally, nanoparticles size effects have been
simulated by Ward-Jones et al.94 for the anodic
stripping voltammetry of various sizes of AgNPs.
Theory has been presented for modeling the
voltammetry produced on stripping the nanoparticles
from the surface of an electrode. Radial diffusion and
the proximity of the particles to each other were
considered in the model. Electrochemical detection of
hydrogen peroxide using an edge-plane pyrolytic-
graphite electrode, a glassy carbon electrode, and a
silver nanoparticle-modified glassy carbon electrode
has been reported by Welch et al.95. The hydrogen
peroxide which could not be detected directly on
either the EPPGE or GCE electrodes in phosphate
buffers was facilitated by modification of the glassy-
carbon surface with nanosized silver assemblies.
Screen-printed electrodes are planar devices with
plastic substrates that are coated with layers of
electroconductive and insulating inks at controlled
thickness. Such an electrode modified with silver
nanoparticles by using electrochemical deposition has
been utilized successfully by Calvo et al96. Carbon
screen-printed electrodes (CSPE) modified with silver
nanoparticles present an interesting alternative in the
determination of lamotrigine (LTG) using differential
pulse adsorptive stripping voltammetry. The
electrodes developed in this work present an
214 INDIAN J CHEM, SEC A, JAN-FEB 2012
environmental-friendly method for the analysis
of LTG. The most important advantage is high
sensitivity in the determination of LTG in real
samples. In fact, the detection limit obtained was less
than the values found when LTG was measured
with carbon and mercury-film carbon screen-printed
electrodes.
Electrochemical study of sodium hypochlorite was
carried out on dendrimer stabilized gold nano particles
modified glassy carbon electrode97. Deposition of gold
nanoparticles on the surface of glassy carbon electrode
was observed by transmission electron microscopy and
X-ray photoelectron spectroscopy. Both anodic and
cathodic peak currents were found to increase after the
deposition of these gold nanoparticles. Gold
nanoparticles modified glassy carbon electrode has also
been used to detect Hg(II) in drinking water, sediments
and pharmaceutical preparations by anodic stripping
voltammetry. Mercury concentrations in the low range
(ng/ml) were easily quantified with high accuracy and
precision98. Further, gold nano particles were deposited
onto the surface of glassy carbon electrode and
potential utility of electrode constructed was
demonstrated by applying it for the analytical
determination of As(III) with low detection limit99 of
2.5 ppb. Gold being very sensitive to Cr(VI), gold
nanoparticles based nanostructured electrode was
developed for detection of ultra trace amount of the
carcinogenic Cr(VI) and evaluated for detection of
Cr(VI) in ground water100. Arsenic is highly toxic and a
novel method for the detection of arsenic(III) in
1 M HCl at gold nanoparticles modified glassy carbon
electrode has been developed101. After optimization, a
limit of detection (LOD) of 0.0096 ppb was obtained
with linear sweep voltammetry (LSV). These results
point towards the applicability of the modified sensor
for detection of arsenic in natural water samples.
Simultaneous determinations of various
biomolecules and drugs have vital importance in
biomedical research. A gold nanoparticle-modified
carbon paste electrode has been used successfully for
the simultaneous determination of acetaminophen and
atenolol102 using differential pulse voltammetry (DPV).
The modified electrode exhibited electrocatalytic
properties towards acetaminophen and atenolol
oxidation with a peak potential of 20.0 and 50.0 mV
lower than that at the bare carbon paste electrode,
respectively. Also, the enhanced peak current response
is clear evidence of the catalytic activity of gold
nanoparticles modified carbon paste electrode towards
oxidation of acetaminophen and atenolol. The large peak
separations obtained using this electrode allows
simultaneous detection of these drugs. Goyal et al.103-107
prepared nanogold modified indiumtin oxide (NGITO)
electrode and deposition of nanogold
(~40 nm) was confirmed by scanning electron
microscopy (SEM).105 The electrode was used for the
individual and simultaneous electrochemical
determination of various drugs and biomolecules
including nandrolone, methylprednisolone, atenolol,
adenosine and adenosine-5’-triphosphate, 5-hydroxy-
tryptamine and 5-hydroxyindoleacetic acid. As such the
electrode is not suitable for reduction and the
determinations are based on the oxidation of target
molecules. Application of the electrode has been
successfully demonstrated by determining these
molecules in human urine and blood plasma. The
common metabolites present in urine and blood did not
interfere. The method using NGITO is simple, fast and
accurate and opens new avenues for quick estimation of
physiologically important compounds. Further, as gold
nanoparticles provide larger conductive area, it leads to
improved electron transfer kinetics and enhancement in
the oxidation current. Also, the amount of nano gold on
the electrode surface affects the electrocatalytic activity
of the modified electrode. The interesting characteristics
of gold nanoparticles diminish if they gather to form
large clusters at the surface of the electrode.
Electrocatalytic oxidation of aspirin and
acetaminophen at cobalt hydroxide nanoparticles
modified glassy carbon electrode was performed by
Houshmand et al.108 using cyclic voltammetry,
chronoamperometry and steady-state polarization
measurements. Voltammetric studies show that in the
presence of drugs, the anodic peak current of low
valence cobalt species increases, followed by a decrease
in the corresponding cathodic current. This indicates that
drugs are oxidized on the redox mediator which is
immobilized on the electrode surface via an
electrocatalytic mechanism. Chronoamperometric
studies showed a large anodic current at the oxidation
potential of low-valence cobalt hydroxide in further
support of the mediated electrooxidation. An
amperometric procedure was successfully applied for
quantification of these drugs in the bulk form and to the
assay of aspirin and acetaminophen in human urine
samples.
Nanofibers
Recently, due to its low toxicity and insensitivity
toward the dissolved oxygen in a solution,
 GOYAL & BISHNOI: SURFACE MODIFICATION IN ELECTROANALYSIS
Bi electrodes have attracted much attention as a new
alternative of common mercury electrode due to their
highly reproducible response109. Platinum and
palladium nanoparticles based graphite nano fibers
were used as cathodic electrocatalysts for proton
exchange membrane water electrolysis for hydrogen
evolution reactions110. Sensitive analytical
methodology was presented at nano TiO2-Au-KI
modified glassy carbon and indium tin oxide electrode
for the investigation of hydrogen peroxide. The
practical utility of the modified electrodes was
examined111 by analyzing the real samples as antiseptic
and contact lens cleaner solution containing H2O2.
Platinum metal is widely used as industrial catalyst
and is found in catalytic converters of vehicles to
remove pollutants from car exhaust fumes. Platinum
wires are often used in electrochemistry as electrodes
owing to their stability and conductivity. Chang et al.112
presented a method for the attachment and structural
growth of platinum nano particles (PtNPs) on indium
tin oxide (ITO). The PtNPs attached ITO (PtNP/ITO)
has been applied for the study of electrochemical
oxidation of methanol and the results are presented in
Fig. 5. It can be seen that the peak current in the case
of PtNP/ITO is much more than other two electrodes.
Mixture of Metal Nanoparticles and Nanotubes
Electrodeposition of metal nanoparticles on carbon
nanotubes has been found very beneficial in
electroanalysis of biologically important molecules. It
has been observed that carbon nanotubes work as
catalyst supporting materials and significantly
enhance the electro catalytic activity of metal
nanoparticles for electrooxidation. These supporting
carbon nanomaterials change the morphology and
electronic structure of metal particles due to which
metal nanoparticles-carbon nanotubes catalysts
exhibit high current density and low overpotential for
electooxidation and can be used in direct methanol
fuel cells113. Incorporation of nanoparticles in CNTs
for modification of electrodes enhances the
electrocatalytic activity in many electrochemical
processes and therefore is suitable for sensing
applications. In particular, the combination of metal
nanomaterials and CNTs for surface modification of
biosensors has proved to be more effective than using
either nanomaterial alone. Hrapovic et al.114 focused
on metal nanoparticles/CNTs nanocomposites for
electrochemical detection of trinitrotoluene (TNT)
and other nitroaromatics. They found that Cu
nanoparticles and SWNT solubilized in Nafion
215
Fig. 5⎯Cyclic voltammograms obtained for 0.1 M methanol
oxidation in the N2-saturated 0.5 M sulfuric solution recorded with
(a) the PtNP/ITO electrode prepared via 24 h of growth, (b) a Pt
bulk electrode and (c) a bare ITO electrode. [Reproduced from
Ref. 112 with permission from American Chemical Society,
Washington DC, USA].
provided the highest sensitivity for TNT with the
detection limit of 1 ppb in tap water, river water and
contaminated soil.
Effect of iron and iron oxide combined with
nanotubes as electrode surface modifier has been
studied by Abolanle et al.115 Electrochemical sensors
using EPPGE modified with single-wall
carbon nanotubes-iron(III) oxide (SWNT/Fe2O3)
nanoparticles have been examined for the sensitive
detection of DA. When compared with the bare
electrode and electrode modified with only nanotubes,
the EPPGE-SWNT-Fe2O3 gave the best response
towards the detection of DA. This electrode was
reliably used to assay DA in its real drug composition.
As can be easily seen from the voltammograms in
Fig 6, the electrodes containing SWNT are associated
with large background (capacitive) current responses,
characteristic of acid-treated SWNT.
The electrochemical behavior of rutin on a
gold nanoparticle/ethylenediamine/multi-wall carbon
nanotubes modified glassy carbon electrode
(AuNPs/en/MWNTs/GCE) was investigated and the
electrochemical parameters of rutin were
calculated116. Rutin effectively accumulated on the
AuNPs/en/MWNTs/GCE. The coexisting substance,
AA, caused no interference to the determination of
rutin. The proposed method was further applied to the
determination of rutin in rutin tablet samples with
satisfactory results. Figure 7 shows the cyclic
voltammograms of rutin at different modified
electrodes. Rutin does not display any redox peak at
the bare GCE (a), which demonstrates the weaker
216 INDIAN J CHEM, SEC A, JAN-FEB 2012

Fig. 6⎯Typical cyclic voltammograms of (i) bare EPPGE, (ii) EPPGE-SWNT, (iii) EPPGE-SWNT–Fe and (iv) EPPGE-SWNT–Fe2O3 in
0.1 M PBS (pH 7.0) containing 2 × 10−4 M dopamine at scan rate = 25 mV s−1. [(a) original; (b) background-subtracted]. [Reproduced
from Ref. 115 with permission from Elsevier, Amsterdam, The Netherlands].

adsorption and slower electrochemical reaction of

rutin on the GCE surface. However, well-defined
redox peaks are seen at the en/MWNTs/GCE (b),
MWNTs/GCE (c) and AuNPs/en/MWNTs/GCE (d) in
0.1 M phosphate buffer solution (pH 3.5). The heights
of the redox peaks were obviously higher at the
AuNPs/en/MWNTs/GCE than at the en/MWNTs/GC
or MWNTs/GCE. The ratio of ipa/ipc was
approximately 1.2, which shows that the electrode
reaction was almost reversible. Nano-gold and
MWNTs are expected to enhance the electron-transfer
rate and increase the participation of rutin in the
electrochemical reaction due to accumulation and
catalytic ability.
Tashkhourian et al.117 reported that silver
nanoparticle-carbon nanotube modified carbon paste
Fig. 7⎯Cyclic voltammograms of 8.0 × 10−5 M rutin in
electrode (Ag/CNT–CPE) exhibits excellent 0.1 M phosphate buffer (pH 3.5) on different electrodes.
electrochemical catalytic activities towards the [(a) bare GCE, (b) en/MWNT /GCE, (c) MWNT/GCE and
oxidation of DA and AA by significantly decreasing (d) AuNPs/en/MWNT/GCE; scan rate 100 mV s−1].
their oxidation overpotentials and enhancing the peak [Reproduced from Ref. 116 with permission from Elsevier,
currents. The peak separation between DA and AA Amsterdam, The Netherlands].
was found to be 67 mV, indicating that the Ag/CNT– this modified electrode in 0.1 M NaOH solution.118
CPE facilitated their simultaneous determination. The peak potential of O2 reduction at the Cu-Au-
Further, multi-walled carbon nanotubes were MWNT/GCE shifted from ca. 70 mV to higher
functionalized with acid treatment and thereafter positive potentials as compared to that of a polished
gold-copper nanoparticles were electrodeposited on bare glassy carbon electrode. Significant current
the MWNT by applying several repetitive scans, enhancement was obtained at Cu-Au-MWNT/GCE as
forming a Cu-Au-MWNT/GCE interface. The compared to that of bare GCE, MWNT/GCE,
electrochemical reduction of oxygen was studied on Cu-MWNT/GCE and Au-MWNT/GCE.
 GOYAL & BISHNOI: SURFACE MODIFICATION IN ELECTROANALYSIS
Electrochemically deposited Pt nano-clusters on
MWNT modified GCE showed a strong
electrocatalytic activity towards the oxidation of
estrogens involving estradiol, estrone, and estriol.119
The electrode showed linear response from 0.5-15 μM,
2.0-50 μM and 1.0-75 μM for estradiol, estrone, and
estriol, respectively using square-wave voltammetry
In comparison with the MWNT/GCE or Pt
nanoparticles modified GCE prepared in a similar
manner, this composite modified electrode exhibited
much higher current sensitivity and catalytic activity.
Wei and co-workers120 used a composite of nano-
silver coated MWNT to determine traces of
thiocyanate in urine and saliva samples from smokers
and non-smokers by cyclic voltammetry with LOD in
nM range. The characterization of nano-silver coated
multi-walled carbon nanotubes was carried out with
SEM and XRD methods. Liu et al.121 designed a
sensor by electropolymerization of thionine at the
GCE modified with gold nanoparticles-multiwalled
carbon nanotubes (GNPs/MWNT) composites for
simultaneous determination of adenine and guanine in
DNA. The modified electrode exhibited enhanced
electrocatalytic behavior and good stability for the
detection of guanine and adenine.
An important catecholamine neurotransmitter is
epinephrine, which is involved in the message transfer
of the mammalian central nervous system. In
biological fluids such as blood and urine, EP coexists
with AA, and UA, which interferes during the
electrochemical detection of EP at conventional
electrodes. Chen’s group122 developed a method for
the simultaneous determination of AA, EP, and UA at
physiologically relevant conditions by using the film
composed of functionalized-MWNT and Nafion
incorporating platinum and gold nanoparticles
modified glassy carbon electrode. A new glucose
electrochemical biosensor has also been designed by
Norouzi et al.123 in which glucose oxidase, the
important sensing material which catalyzes the
oxidation of glucose was immobilized on to gold nano
particles and MWNT modified glassy carbon
electrode. The electrode was found to exhibit an
outstanding and reproducible sensitivity for glucose
oxidation. Electrochemical sensing of adenine was
studied at SnO2 nanoparticles modified carbon paste
electrode. The coupling of these nanoparticles with
carbon paste brought in some advantages such as an
improved voltammetric response of adenine with high
sensitivity and selectivity. The modified electrode was
217
successfully utilized to detect specific nucleic acid
hybridization and for monitoring of some proteins124.
Preparation and characterization of nano-copper
coated multi-walled carbon nanotubes modified
glassy carbon electrode (Cunano/CNTs–Nf/GCE) for
the determination of nitrite was demonstrated by
Yang et al.125 In this work, Cu nanoparticles were
electrodeposited onto the film of Nafion-solubilized
multi-walled carbon nanotubes deposited on GCE.
The resulting Cunano/CNTs–Nf/GCE exhibited
excellent electrocatalytic activity towards the
reduction of nitrite. The simplicity, low detection
limit, low applied potential, high sensitivity, fast
response time and wide linear range is attributed to
the synergistic effect of CNTs and Cu nanoparticles.
The electrochemical decoration of EPPGE with
cobalt and cobalt oxide nanoparticles integrated with
single-walled carbon nanotubes (EPPGE–SWNT–Co)
was presented by Adekunle et al.126 The current
response of the EPPGE–SWNT–Co towards nitrite
was approximately 3 folds higher than that of bare
electrode (Fig. 8a) with slightly lower onset potentials
(0.78 V). At pH 3.0, the EPPGE-SWNT–Co exhibits
faster catalysis as compared to EPPGE-Co (less
positive potential, 100 mV lower than Co electrodes
without SWNT), although the current response was
almost the same. It is evident from Fig. 8(a) that the
oxidation potential was lower with high current
response on the EPPGE–SWNT–Co nanoparticles
modified electrode. The better electrooxidation
reaction of the EPPGE–SWNT–Co can be attributed
to the SWNT itself acting as an electrical conducting
nanowire which enhances electron transport between
the base electrode and analyte.
The integration of nano ZnO and MWNT has been
explored by Zhang et al.127 to enhance the
electrochemical signal of DNA and increase the
detection sensitivity. The remarkable synergistic
effect of the zinc oxide nanoparticles and multi-
walled carbon nanotubes for the ssDNA probe
immobilization was observed. The simple
modification procedure, high selectivity, low cost, fast
response and broad linear range are the main features
of the proposed DNA biosensor.
Ghalkhani et al.128 utilized MWNT decorated
with silver nanoparticles (AgNPs-MWNT) as an
effective strategy for modification of the surface of
pyrolytic graphite electrode by colloidal dispersion of
decorated MWNT in water to obtain uniform and
stable thin films for altering the surface properties of
218 INDIAN J CHEM, SEC A, JAN-FEB 2012

Fig. 8⎯Comparative current response (after background current subtraction) of the EPPGE, EPPGE–SWNT,EPPGE–SWNT–Co and
EPPGE–SWNT–CoO in (a) 1 mM nitrite solution in pH 7.4 PBS and (b) 1 mM nitrite solution in pH 3.0 PBS. [Scan rate = 25 mVs−1].
[Reproduced from Ref. 126 with permission from Elsevier, Amsterdam, The Netherlands].

the working electrode. Comparative study of

electrochemical behavior of sumatriptan (Sum) at
bare PGE and AgNPs-MWNT modified electrode
indicates that the AgNPs-MWNT modified PGE
significantly enhanced the oxidation peak current of
Sum. A remarkable enhancement in microscopic area
of the electrode together with strong adsorption
of Sum at the surface of the modified electrode
resulted in a considerable increase in the peak current
of Sum. A carbon nanotube modified electrode is
made by Streeter et al.129 in which a glassy carbon
electrode is partially covered with a layer of gold
nanoparticle-modified CNTs as presented in Fig. 9. Fig. 9⎯Schematic diagram of gold-modified MWNT randomly
The carbon surfaces are passivated by the distributed on a glassy carbon macroelectrode. [Reproduced from
physisorption of anthraquinone-2, 6-disulfonic acid so Ref. 129 from permission of American Chemical Society,
that only the gold nanotubes can be electroactive. Washington DC, USA]
Linear sweep voltammetry of ferrocyanide has been
studied using this modified electrode, and the results detailed comparison has been made among the
interpreted by numerical simulation. It is shown that voltammetric response of bare ITO, MWNT/ITO and
the voltammetric determinations can measure the total AuNP-MWNT/ITO in respects of several essential
length of the CNTs present on the surface. The effect analytical parameters viz. sensitivity, detection limit,
of surface modification of indium tin oxide (ITO) by peak current and peak potential of tryptophan.
MWNT and gold nanoparticles attached MWNT has
been studied recently to determine tryptophan, an Ionic Liquid/Carbon Paste
important and essential amino acid for humans and Ionic liquids (ILs) present a high degree of
herbivores130. A comparison of SEM images as shown asymmetry that inhibits crystallisation at room
in Fig. 10 clearly indicates the deposition of MWNT temperatures. ILs posses some fascinating properties
and Au nano particles on the surface of ITO. A including nonvolatile nature, low melt point, strong
 GOYAL & BISHNOI: SURFACE MODIFICATION IN ELECTROANALYSIS
Fig. 10⎯Typical FE-SEM images observed for (A) MWNT/ITO, (B) AuNP-MWNT/ITO and (C) bare ITO surfaces. [Reproduced from
Ref. 130 with permission from Elsevier, Amsterdam, The Netherlands].
electrostatic field, high polarity, favourable viscosity
and density as solvents, high thermal stability and the
ability to solvate a wide range of species including
organic, inorganic, and organometallic compounds.
Due to the unique features such as wide potential
windows (a voltage range between which the
electrolyte is not oxidized or reduced) and high
electrical conductivity, hydrophobicity, insolubility in
water and plasticizing ability, ILs are used in
construction of electrochemical sensors and
biosensors. ILs have shown good compatibility with
biomolecules and enzymes, and even whole cells.
Thus, ILs can be used in electrochemical biosensors
typically as both binder and conductor. The difference
between the potentials of their anodic (Ea) and
cathodic (Ec) decomposition131 is usually greater than
3 V, while for aqueous electrolytes it is about 1.2 V.
Because of this remarkable property of ionic liquids,
they find wide use in electrochemical biosensors.
Electrochemical properties of ionic liquids
The unique properties of ILs can be tailored by
combining different cations with suitable anions. The
fact that ILs are intrinsically good ion conductors and
generally of very low vapor pressure makes them
attractive as device electrolytes. The viscosity of an
IL is an important consideration in electrochemical
studies due to its strong effect on the rate of mass
transport within solution. ILs generally are more
viscous than most molecular solvents due to the large
internal friction of fluids. Viscosity of the ILs depends
on the temperature and impurities present in the ILs.
The addition of co-solvent such as, water, acetonitrile,
acetone, alcohol, dichloromethane, benzene and
toluene can result in a dramatic decrease in viscosity
of ILs. Typically, ILs have a potential window of
219
more than 2.0 V. However impurities in the ILs have
a profound impact on the anodic or cathodic potential
limits and the corresponding electrochemical potential
window. The large potential window of ILs makes
them significant as electrolytes for electrodeposition
of metals. This property also permits stable
electrochemical cycling of intrinsically conductive
polymer electrodes that have been widely used in
applications including electrochemical sensors.
Various electrochemical sensors using ILs as a
functional media have been developed. Maleki
and co-workers132 developed a sensor with
electrochemical properties that would be well suited
for use in sensor and biosensor applications.
N-octylpyridinium hexafluorophosphate, [Opyr] [PF6],
was used as a binder of graphite powder in the
construction of a carbon paste electrode. The authors
claim several advantages by using this composite
electrode including increment in electron-transfer rate
and marked decrement in overvoltage for
biomolecules such as NADH, dopamine and ascorbic
acid. The composite electrode circumvents NADH
surface fouling effects. Also, higher current densities
for a wide range of compounds are observed. All
these properties indicate it to be a sensitive, simple,
and stable composite electrode for the detection of
biomolecules and other electroactive compounds.
Zhu et al.133 described the potential application of
MWNT/AuNP/IL composite electrode for the
fabrication of a non-enzymatic glucose sensor. The
AuNPs embedded in MWNT/IL gel show strong and
sensitive voltammetric response to glucose, owing to
a possible combined synergistic effect of AuNPs,
MWNT and IL. The simultaneous determination of
dopamine, ascorbic acid and uric acid has been
developed by Safavi et al.134 It was observed that
220 INDIAN J CHEM, SEC A, JAN-FEB 2012
the apparent reversibility and kinetics of the
electrochemical reaction at the carbon ionic liquid
electrode (CILE) was significantly enhanced as
compared to those obtained using a conventional
carbon paste electrode. The same group has fabricated
a non-enzymatic composite electrode by mixing
nano- Ni(OH)2 with graphite powder and [Opyr][PF6],
which showed excellent electocatalytic activity towards
oxidation of glucose in an alkaline solution135 .
A composite electrode based on mixing
nano copper(II) hydroxide with graphite powder and
[Opyr][PF6] was successfully utilized by Safavi et al.136
for the simultaneous electrochemical detection of
glutathione and glutathione disulfide. Application of
copper(II) hydroxide in the composite electrode
results in complexation of Cu(II) with the thiol group
of glutathione and leads to a significant decrease in
glutathione oxidation overpotential, while an anodic
peak corresponding to the direct oxidation of
glutathione disulfide as the product of glutathione
oxidation is observed at higher overvoltages. An
ethanol biosensor has been developed137 based on the
lithium methylsulfonyl group-containing IL prepared
from the precursors, poly(propylene glycol)-block-
(ethylene glycol)-block-(propylene glycol)-bis(2-
aminopropyl ether) with varying molecular weight
(600, 900, and 2000 g/mol, commercially denoted as
Jeffamine ED-600, ED-900, and ED-2000,
respectively). To determine the sensitivity of the
sensor, these liquids are analyzed with nickel
electrodes, where a redox reaction of the
Ni(OH)2/NiOOH couple was observed. Further,
Tu et al.138 used a composite material based on
SWNT, a water-insoluble porphyrin (hydroxyl-
ferriprotoporphyrin, hematin) and 1-butyl-3-
methylimidazolium hexafluorophosphate ([bmim] [PF6])
to modify a GCE to study the direct electrochemistry
and electrochemical properties of porphyrin. The
porphyrin dissolved in [bmim][PF6] was self-
assembled on SWNT by π–π non-covalent interaction,
which leads to good dispersion of the SWNTs in the
[bmim][PF6] and a direct electrochemical response
corresponding to the Fe3+/2+ redox couple. This study
provides a facile way for preparing biofunctional
materials, accelerating electron-transfer, and
extending the application of porphyrins/IL-based
composite materials in sensor applications. Wang et al.139
fabricated an electrode by mixing
room temperature ionic liquid, 1-butyl-3-methyl-
imidazolium tetrafluoroborate, and MWNT along
with chitosan. The use of ionic liquid and MWNT at
the electrode surface increases ionic and electrical
conductivities, thus enhancing the sensitivity of the
sensor for NADH sensing139.
Recently, a colloidal gold-modified carbon ionic
liquid electrode was constructed by mixing colloidal
gold-modified graphite powder with a solid RTIL,
n-octyl-pyridinium hexafluorophosphate (OPPF6)140.
The electrode showed good bioactivity and excellent
stability. The sensor was capable of distinguishing the
complementary target DNA at low concentration from
the three-base mismatched DNA at higher
concentration. A room-temperature ionic liquid,
N-butylpyridinium hexafluorophosphate, was used as
a binder to construct an ionic liquid modified carbon
paste electrode, which was characterized by scanning
electron microscopy and electrochemical impedance
spectroscopy141. The ionic liquid carbon paste
electrode (IL-CPE) showed enhanced electrochemical
response and strong analytical activity towards the
electrochemical oxidation of dopamine. The IL-CPE
was sensitive, selective and showed good ability to
distinguish the coexisting ascorbic acid and uric acid.
Figure 11 clearly indicates that the oxidation process
of dopamine using the IL-CPE is greatly improved.
One attractive approach to using ionic liquids with
carbon nanotubes in biosensors involves the use of
multiwall carbon nanotubes ionic liquid modified
glassy carbon electrode (MWCN-ILs/GCE). In this
approach, MWNT were thoroughly mixed with the
ILs by grinding in a mortar to create a gel-like paste
a Fig. 11⎯Cyclic voltammograms of 1.0×10−4 mol/L dopamine (DA)
on the CPE (a) and the IL-CPE (b) with a scan rate of
50 mV/s. [Reproduced from Ref. 140 with permission from
Springer, Germany]
 GOYAL & BISHNOI: SURFACE MODIFICATION IN ELECTROANALYSIS
Fig. 12⎯Cyclic voltammograms of (a) 1.0 mM UA at bare GC
electrode and (b) 1.0 mM UA at MWNT-IL-gel/GC electrode.
[Reproduced from Ref. 142 with permission from Elsevier,
Amsterdam, The Netherlands].
which was then applied to the surface of a cleaned
glassy carbon electrode. Cyclic voltammograms of
dopamine solutions were recorded using a platinum
wire and a saturated calomel electrode as auxiliary
and reference electrodes, respectively. An immediate
advantage of the MWCN-ILs was found to be the
larger peak current with smaller peak separations, an
indication of faster electron transport to the electrode
surface142. Figure 12 clearly indicates that peak
current of uric acid increased significantly by using
MWNT-IL-gel/GCE as compared to bare GCE. The
modified electrode has been successfully applied for
the assay of DA in human blood serum.
A nanocomposite material consisting of amine
functionalized multi-walled carbon nanotubes and a
room temperature ionic-liquid, 1-butyl-3-methyl-
imidazolium tetrafluoroborate, was reported for use in
construction of a novel catalase based biosensor for
the measurement of hydrogen peroxide143. The
modified electrode exhibited a quasi-reversible cyclic
voltammogram corresponding to the Fe(II)/Fe(III)
redox couple in the heme prosthetic group of catalase.
The nanocomposite film showed an obvious
promotion of the direct electron transfer between
catalase and the underlying electrode. Recently,
Zhao et al. 144 proposed a novel strategy for
investigating the electrical-ionic properties of RTILs
and carbon composite materials formed by mixing a
water-insoluble IL [bmim] [PF6] and carbon materials
of two types, one of which was MWNT with a tube
shape and the other meso-carbon micro-beads
(MCMB). The hybrid MWNT/RTIL and
MCMB/RTIL materials showed a different
221
conductivity mechanism as determined by ac
impedance. The ILs and carbon composite materials
can also be used as modifiers in the direct
electrochemistry of protein. [bmim][PF6]-single-
walled carbon nanotubes gel modified glassy carbon
electrode (bmimPF6-SWNT/GCE) was fabricated to
determine p-nitroaniline (PNA). The feasibility to
determine other nitroaromatic compounds (NACs)
with the modified electrode was also tested. Under the
optimized conditions, the peak current was linear to
NACs concentration and the detection limits down to
nanomolar level, which are better than the values
obtained by using carbon materials based electrodes
without RTILs 145.
A voltammetric method was developed for the
determination of tetracycline (TC) using an ionic liquid
(1-octyl-3-methylimidazolium-hexafluorophosphate)–
multiwalled carbon nanotubes film coated glassy
carbon electrode146. The results indicate that both IL
and MWNT can facilitate the TC oxidation with good
reproducibility. Zhang et al.147 developed a RTIL
supported three-dimensional network SWNT
electrode. The glucose oxidase was directly
covalently anchored on the SWNT-poly-N-
succinimidyl acrylate assembly. The application of
the RTIL-supported three-dimensional network
SWNT electrode overcame the difficulties of
homogeneous electrochemical functionalization of
SWNTs in large quantities. Salimi et al.148 have
recently reported a new carbon nanotubes-ionic liquid
and chloropromazine modified electrode for the
determination of NADH. The nanocomposite
modified electrode displays excellent electrocatalytic
activity towards the oxidation of NADH. The
proposed electrode has potential application in the
third generation reagentless biosensor. The
composites of SWNT, gold nanoparticles and ionic
liquid (1-octyl-3-methylimidazolium hexafluoro-
phosphate) were used to fabricate a modified GCE for
the sensitive voltammetric detection of
chloramphenicol.149 The composition of the film
affected the detection limit and was found to be
5.0 nM under optimum conditions.
Concluding Remarks
Various approaches for the surface modification of
electrodes are available these days with their
advantages and limitations. It is reasonable to use
current density (current per surface area) to evaluate
the performance of sensors. The ideal case is that in
which the layer is permeable to target compounds,
222 INDIAN J CHEM, SEC A, JAN-FEB 2012
while resistant to the interfering compounds. For
surface modification approaches aimed at enhancing
the performance of sensors, four factors should be
considered: (1) enlarged surface area. Both carbon
nanotubes and metal nanomaterials increase the
effective surface area of the electrodes; (2) enhanced
electron transfer rate due to the catalytic ability of
nanomaterials. The electron transfer and adsorption
reactivity of graphitic carbon electrodes depends
strongly on the surface coverage of edge relative to
basal plane graphite, with the edge sites more reactive
to electron transfer, adsorption and chemical
modification; (3) Redox systems differ dramatically in
their sensitivity to the state of the carbon electrode
surface, due to differences in their redox reaction
mechanisms, ionic charge, etc. Consequently, certain
standards should be set up to evaluate the performance
of the sensors. It is recommended that for a particular
target a specific sensor exhibits optimal response. It is
unwise and often incorrect to discuss “activation” of a
carbon electrode without stating the redox reaction
used as the indicator of electrode reactivity; (4) Carbon
materials vary more in both bulk and surface structures
as compared to metals, hence procedure for electrode
preparation is particularly important in the case of
carbon materials for achieving reproducible
electrochemical behavior. Even the most common
preparation procedures, such as polishing, significantly
modify the surface structure and chemistry and can
have dramatic effects on reactivity and adsorption.
In the future, more developments in applications of
ionic liquids in electrochemistry are expected. The
simple dissolution of a lithium salt always results in
electrolytes in which only a fraction of the current is
actually carried by Li+ ions. It would be interesting to
see whether the incorporation of lithium salts with a
polyanionic chain, through specific interaction with the
fixed negative charge of polarizing Li+ ions, can
change the flux balance. All of these fundamental
aspects of the physical chemistry and electrochemistry
of ionic liquids remain to be thoroughly explained, and
hold the promise to further improve their potential in
various electrochemical applications.
New strategies for the synthesis of nanostructered
metal oxide-based sensors are likely to result in new
bioelectronic sensing applications. Functionalizing
nanostructered metal oxide-based sensors with the
desired groups to bind target biomolecules, and
doping these with electronically active materials to
obtain enhanced charge transfer, may lead to
innovative methods in sensor development. The
synthesis of nanoparticles with various morphologies at
the nano domain level may offer a suitable
environment for oriented immobilization of the desired
biomolecules and thereby amplified signals. These
nanostructered metal based sensors can be fabricated
and tested in desired patterns for the development of
functional integrated devices. The interface of
nanomaterial based devices could also be used for
parallel real-time monitoring of multiple analytes. It
will be interesting to focus on new methods for the
fabrication of innovative sensors with desired
properties for health care and confining different
biomolecules by using metal nanomaterials and their
nano-structured oxides.
The implication of nanomaterials in electroanalysis
is due to very specific properties of nanomaterials,
exhibited only at the nanoscale. These include
enhanced diffusion based on convergent rather than
linear diffusion, high active surface area, improved
selectivity, catalytic activity, higher signal-to-noise
ratio and unique optical properties. The use of
nanomaterials also grants control over the local
microenvironment. This can be vastly profitable while
incorporating sensitive or biological material into a
system. These unique properties make nanomaterials
extremely suited for electroanalytical applications.
Improved convergent mass transport to nanoelectrodes
assists the study of faster electrochemical processes. At
the nanoscale, crystal planes can be exposed which are
not accessible at the macroscale, in turn giving rise to
enhanced current responses and catalysis. In terms of
construction of nanomaterial based electrodes, costs
can be reduced compared with the costs for
manufacture of conventional macroelectrodes as only a
fraction of the nanomaterial is needed. Therefore, the
electroanalytical application of such nanomaterials has
been found to be quite extensive which clearly
indicates that there is a large scope for further study in
this area of electrochemistry.
Acknowledgement
One of the authors (RNG) is thankful to CSIR,
New Delhi, DST, New Delhi and DBT New Delhi for
their constant research support through funding of
different projects.
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