Talanta 55 (2001) 773 782

www.elsevier.com/locate/talanta

Tetraphenylborate doped polyaniline based novel

pH sensor and solid-state urea biosensor
Prem C. Pandey *, Govind Singh
Department of Chemistry, Banaras Hindu Uni6ersity, Varanasi 221 005, India
Received 17 February 2001; received in revised form 2 July 2001; accepted 3 July 2001

Abstract
A novel pH sensor suitable for use in both aqueous and non-aqueous mediums is reported. The sensor is derived
from polymer modified electrode obtained from electrochemical polymerisation of aniline in dry acetonitrile
containing 0.5 M tetraphenyl borate at 2.0 V versus Ag/AgCl. The light yellow colour polymer modified electrode
obtained under the present experimental condition has been characterised by scanning electron microscopy (SEM).
The pH sensing of polymer modified electrode in both aqueous and non-aqueous mediums is examined and reported.
As the typical examples, we used weak acid (acetic acid) and weak base (ammonium hydroxide) as analytes. The
acetic acid is analysed in both aqueous and dry acetonitrile whereas ammonium hydroxide is analysed only in
aqueous medium. The analysis in aqueous medium is conducted in 1 mM Tris HCl buffer pH 7.0 and also in 0.1 M
KCl. The slope of pH sensing is calculated from the data recorded in typical buffers and found to be  86 mV per
pH. The application of polymer modified electrode for the construction of urea biosensor is described based on
immobilised urease within poly vinyl alcohol (PVA) matrix and also within organically modified sol-gel glass on the
surface of polymer-modified electrode. The new urea sensor has shown maximum response of 160 mV at 25 C with
a lowest detection limit of 20 mM. The performance of new pH sensor and urea sensor has been studied and reported
in this communication. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Biosensor; Ion-exchanger; Electrode

1. Introduction
There still exist a need of new pH sensor suitable for use in both aqueous and non-aqueous
mediums since the conventional glass electrode
has known limitations. Several of such limitations
can be eliminated if solid state pH sensitive elec* Corresponding author. Tel.: + 91-542-317-745; fax: + 91542-368-174.
E-mail address: p c pandey@satyam.net.in (P.C. Pandey).

trode could be designed with relatively less technical expertise and low cost. During recent years,
reports on the development of solid-state ion-selective electrodes has gained attraction of world
scientists [15]. The solid-state configuration of
pH sensitive electrode replacing glass membrane is
although available which require technical expertise, high cost and not very well suited for commercial developments [69]. Further advanced
miniaturised technological developments based on
field-effect transistors (ISFETs) are also available

0039-9140/01/$ - see front matter 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 0 3 9 - 9 1 4 0 ( 0 1 ) 0 0 5 0 5 - 7

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P.C. Pandey, G. Singh / Talanta 55 (2001) 773782

again leading to least viability for practical and

commercial designs [10].
During last decade, efficient efforts have been
given on the developments of pH transducer
based on polymer modified electrode. A number
of organic materials have been tested as potential pH transducers [11 18]. Amongst the various materials, polyaniline has been found most
suitable for pH sensing in aqueous medium [15
18]. The synthesis of this polymer was conducted in aqueous acidic medium and again was
limited for their use in aqueous medium. Recently, an advanced pH transducer based on
processible polyaniline was reported which was
again limited for applications in aqueous
medium only as the polymer was initially synthesised in aqueous acidic medium followed by
processing on metal surface by dissolving the
polymeric material together with other additives
in chloroform and subsequently assembling the
resulting solution on electrode surface [18]. We
have also recently developed a solid-state poly
(3-cyclohexyl) thiophene treated electrode as pH
sensor and subsequently urea sensor [5]. There
are some major problems on the development of
this pH sensor at commercial scale and these
are (1) relatively complex synthesis protocol of
3-cyclohexyl thiophene; (2) less stability of 3-cyclohexyl thiophene under ambient conditions; (3)
solubility of poly (3-cyclohexyl) thiophene in
several organic solvents; (4) poor electrochemical
communication of polymer modified electrode
obtained through self evaporation of excess solvent after laying down a drop of polymer solution on solid surface [5,18].
The design of solid-state ion-selective electrode (ISEs) has recently attracted the incorporation of ion-exchanger in polymer matrix [1,2].
The incorporation of ion-exchanger within polymer generate symmetric cell configuration [ion-in
and ion-out] for generating constant dipolar potential essentially required for baseline recovery
during potentiometric operation. We have also
reported few ISEs in solid-state configuration
using conventional ionophore assembled on anions doped conducting polymers [3,4]. These
contributions attracted our attention on the incorporation of tetraphenylborate (TPB), a

known non-specific relatively hydrophobic ionexchanger, within the polymer interecess. We

found remarkable observation on the electrochemical synthesis of polyaniline in dry acetonitrile containing TPB. The new polymer is
sensitive enough with retaining reproducibility
for more than 9 months (without loss of potentiometric response) while using in both nonaqueous and aqueous medium. The present
research investigation shows much better novelty
over the existing problems of earlier reported
pH sensor [5,18]. The new pH sensor has been
exploited in the construction of solid-state urea
biosensor by immobilising urease within poly vinyl alcohol (PVA) on polymer modified electrode. The new urea biosensor is found to have
better sensitivity. The new polymer modified
electrode has also been used in non-aqueous
medium using acetic acid as an analyte. The results on these lines are reported in the present
communication.

2. Experimental section

2.1. Reagents
Dry acetonitrile (HPLC grade) acetic acid,
PVA and sodium tetraphenylborate was obtained from E. Merck, Germany, aniline as obtained from Aldrich was distilled under vacuum
before use.

2.2. Electrochemical set-up

The electrochemical measurements were performed using Electrochemical Interface (Solartron, 1287) connected to a PC through serial
port. The working electrode used for the construction of electropolymerised polymer was
made from a Teflon cylinder as described earlier
[35]. All electrochemical experiments were carried out in a three-electrode single-compartment
cell with a working solution volume of 5 ml
equipped with a working electrode; Ag/AgCl
reference electrode and a platinum foil auxiliary
electrode. The working solution was made by
dissolving 0.5 M tetraphenylborate (TPB) con-

P.C. Pandey, G. Singh / Talanta 55 (2001) 773782

taining 0.4 M aniline in dry acetonitrile. The

electropolymerisation was carried out potentiostatically, at 2.0 V versus Ag/AgCl with a reference solution of same electrolyte, for 10 min. A
light yellow colour polymer appeared on working electrode. The polymer-modified electrode
was washed 10 times in dry acetonitrile to remove traces of oligomer, monomer and TPB
and was subsequently used as such for pH sensing.

2.3. Construction of urea biosensor

The urea biosensor was made following two
protocols of urease immobilisation on polymermodified electrode. The urease was purified as
described earlier [19].

2.3.1. Protocol (1)

The urease solution (200 ml; 35 mg ml 1; specific activity 200 U mg 1)) in 1 mM Tris HCl
buffer (pH 7.0) was mixed with 100 ml 5% PVA
(MW 125 000). Then, 30 ml of this solution was
applied over polymer modified electrode and allowed to solidify for 16 h at 4 C. The enzyme
electrode was thoroughly washed in 1 mM
TrisHCl buffer pH 7.0 and stored in dry condition at 4 C when not in use.
2.3.2. Protocol (2)
The urease solution (30 ml; 35 mg ml 1; specific activity 200 U mg 1)) in 1 mM Tris HCl
buffer (pH 7.0) was added over polymermodified electrode and allowed to adsorb for 12
h at 4 C. On the next day, the organically
modified sol gel glass layer (ormosil) layer was
assembled over adsorbed urease on polymermodified electrode. The composition of sol-gel
glass precursors was 3-aminopropyltriethoxysilane (70 ml); 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane (20 ml); distilled water (700 ml);
polyethylene glycol (2 mg ml 1) and 0.1 M HCl
(5 ml). After thorough homogenisation of sol
gel precursors; 40 ml of the solution was then
assembled over adsorbed urease layer and gelation was followed for 24 h to form ormosil
layer over the enzyme-modified polymer layer.
The ormosil covered layer was then incubated in

775

1 mM Tris HCl buffer pH 7.0 for 612 h in

order to remove any water soluble components
of modified enzyme electrode. The enzyme electrode was thoroughly washed in 1 mM Tris
HCl buffer pH 7.0 and stored in dry condition
at 4 C when not in use.

2.4. The potentiometric measurements

The electrodes were inserted in single compartment, double wall electrochemical cell containing
suitable
non-aqueous
(acetonitrile
containing 0.1 M TPB) or aqueous working solution (1 mM Tris HCl buffer pH 7.0). The
working and reference electrodes were connected
to Keithley multi-meter (model 2000) followed
by interfacing to a PC through serial port. At
the steady-state response, varying concentrations
of suitable acid/base were injected and data
were recorded. The electrochemical cell assembly
for the acid/base sensing was as follows:
polymer modified electrode/1 mM Tris HCl
buffer (pH 7.0)/Ag/AgCl (containing 3 M NaCl
solution saturated with AgCl);
or,
polymer modified electrode/0.1 M KCl/Ag/
AgCl (containing 3 M NaCl solution saturated
with AgCl).
The electrochemical cell assembly for the urea
sensing using enzyme electrode was as follows:
enzyme electrode/1 mM Tris HCl buffer (pH
7.0)/Ag/AgCl (containing 3 M NaCl solution
saturated with AgCl).
The electrochemical assembly in non-aqueous
medium was as follows:
polymer modified electrode/0.1 M TPB in acetonitrile/Ag/AgCl (containing 0.1 M TPB in
acetonitrile).

2.5. Scanning electron microscopy of

tetraphenylborate doped polyaniline
The polymer was characterised by scanning
electron microscopy. The polymer was made on
Pt surface and analysed using JEOL-JSM 840A
scanning electron microscope (SEM) at 10 000
magnification.

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P.C. Pandey, G. Singh / Talanta 55 (2001) 773782

3. Results and discussion

3.1. Spectroscopic characterisation of

tetraphenylborate doped polyaniline
The polymer was analysed by SEM. Fig. 1
shows the SEM of the polymer at 10 000 magnification. The polymeric domains are symmetrical
and the growth of the polymer seems to be different than those reported earlier for conventional
polyaniline made in aqueous acidic medium. As
already reported, the PAn film prepared in
aqueous HClO4 solution has a fibrous structure
and the polymer chain grows favourably without
oligomer flow, resulting large size grains from
higher acid content solution [20,21]. The polymergrowth under the present experimental conditions
has aggregate rod shaped structure with smooth
surface and least-porosity. This difference in the
film-structure may be due to the difference of film
growing rate, the non-polarity of the solvent and
the lipophilic-dopant. The least porosity may create diffusion-limited boundaries at polymer solution interface.

3.2. The pH sensing beha6iour of

tetraphenylborate doped polyaniline- modified
electrode
The pH sensing behaviour of polymer-modified
electrode is basically the function of proton con-

Fig. 1. Scanning electron microscopy of tetraphenyl doped

polyaniline at 10 000 magnification.

centration and subsequent interaction of protons

with the polymer-film. The proton concentration
of an acid or a base after the addition of the same
in a working solution is dependent on: (1) kinetics
of dissociation of an acid or a base in working
solution; and (2) the buffering action of working
solution in which measurement is being made.
Since the kinetics of dissociation of strong acid or
strong base is greater than that of weak acid or
weak base under similar working solution, we
studied the sensing of both strong acid/strong
base (HCl/NaOH) and weak acid/weak base (acetic acid/NH4OH). Secondly for practical applications of a pH sensor, normally a buffering system
is required accordingly, the buffering capacity of
working solution need to be seriously considered
during pH sensing. We chose two working solutions, the first one with a buffering capacity (1
mM Tris HCl buffer pH 7.0) and the second one
being an electrolyte solution (0.1 M KCl), a nonbuffering working solution. First, we monitored
the typical proton sensing-behaviour of new polymer modified electrode in 1 mM TrisHCl buffer
pH 7. Fig. 2a shows the typical response of the
sensor on addition of increasing concentrations of
acetic acid in 1 mM TrisHCl buffer pH 7.0.
Since the measurements were made in a working
solution with some buffering action, the initial
dissociation of acetic acid into free proton would
be relatively small. Accordingly, the initial potentiometric response on the addition of acetic acid is
non-linear and subsequently increases as a function of acetic acid dissociation in working solution. The inset to Fig. 2a shows the calibration
curve for acetic acid analysis. Subsequently, the
pH sensing of polymer-modified electrode to
strong acid (HCl) was also investigated in the
same working solution. Fig. 2b shows the typical
response of the sensor of the addition of increasing concentrations of HCl in 1 mM TrisHCl
buffer pH 7.0. The sensitivity of analysis is better
when strong acid was added to same working
solution (Fig. 2b) as compared with sensitivity
recorded in Fig. 2a recorded on the addition of
weak acid. The inset to Fig. 2b shows the calibration curve for HCl analysis. Based on these arguments, we also investigated the response of
strong/weak base in 1 mM TrisHCl buffer pH

P.C. Pandey, G. Singh / Talanta 55 (2001) 773782

777

calibration curves for NH4OH and NaOH analysis, respectively. Again similar observation on sensitivity of base sensing was recorded as was
observed in case of strong and weak acid. Further, the response of weak base is greater (Fig. 3a)
as compared with that of weak acid (Fig. 2a),

Fig. 2. (a) Typical potentiometric response of polymer

modified electrode on the additions of increasing concentrations of acetic acid in 1 mM Tris HCl buffer pH 7.0. The
inset to Fig. 2a shows the calibration curve for acetic acid
analysis. (b) Typical potentiometric response of polymer
modified electrode on the additions of increasing concentrations of HCl in 1 mM Tris HCl buffer pH 7.0. The inset to
Fig. 2b shows the calibration curve for HCl analysis.

7.0. Fig. 3a shows the typical response of the

sensor of the addition of increasing concentrations of ammonium hydroxide in 1 mM TrisHCl
buffer pH 7.0. Similarly, Fig. 3b shows the typical
response of the sensor of the addition of increasing concentrations of NaOH under similar conditions. The insets to Fig. 3a and b shows the

Fig. 3. (a) Typical potentiometric response of polymer

modified electrode on the additions of increasing concentrations of ammonium hydroxide in 1 mM Tris HCl buffer pH
7.0. The inset to Fig. 3a shows the calibration curve for
NH4OH analysis. (b) Typical potentiometric response of polymer modified electrode on the additions of increasing concentrations of NaOH in 1 mM Tris-HCl buffer pH 7.0. The inset
to Fig. 3b shows the calibration curve for NaOH analysis.

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P.C. Pandey, G. Singh / Talanta 55 (2001) 773782

Fig. 4. Typical potentiometric response of polymer modified

electrode on the additions of increasing concentrations of
acetic acid in 0.1 M KCl. The inset to Fig. 4 shows the
calibration curve for acetic acid analysis.

which may be possibly due to the reasons (a)

the variation in dissociation constant of weak acid
and weak base in working solution; and (b) sensitivity of the pH sensor to base in a relatively
wider concentration range. The response of pH
sensor to strong acid and strong base has similar
magnitude at same molarity, however, the sensitivity of the sensor has again wider concentration
range for base.
In order to study the pH sensing without
buffering action of working solution (the dissociation of acid/base is independent on working solution), we monitored potentiometric response in
0.1 M KCl. Fig. 4 shows the typical response of
the sensor of the addition of increasing concentrations of acetic acid in 0.1 M KCl. The magnitude
of potentiometric response is greater than that
recorded in 1 mM Tris HCl buffer pH 7.0. This
is mainly due to relatively faster dissociation of
acid/base in electrolyte solution as compared with
that of the same under buffering action (in 1 mM
TrisHCl, pH 7.) The similar results on ammonium hydroxide sensing are shown in Fig. 5. The
insets to Fig. 4 and Fig. 5 show the calibration
curves for acetic acid and ammonium hydroxide
analysis in 0.1 M KCl.

Since the response of the glass electrode is

temperature dependent, we investigated the temperature dependence of potentiometric response
of polymer-modified electrode. The results observed at 20, 30 and 40 C on addition of the
same concentration of acid were 77, 78 and 81
mV, respectively. The data on temperature dependence of polymer-modified electrode is negligible
as compared with the data on temperature dependence of glass electrode. This again justify that the
present sensor works better than that of glass
electrode as a function of temperature. Further,
we investigated the effect of foreign ions on the
potentiometric response of the sensor. We used
same concentration of NaCl, KCl and CaCl2 in
0.1 M KCl. The data show negligible responses to
these ions. Under similar conditions, 1, 2
and 6 mV differences were recorded on the
addition NaCl, KCl and CaCl2, respectively.
These observations justify the novelty of new
polymer-modified electrode for practical applications. The reproducibility of pH sensing of polymer modified electrode is found to be excellent.
The polymer electrode retains 100% electrode response for 6 months of at least the testing period.

Fig. 5. Typical potentiometric response of polymer modified

electrode on the additions of increasing concentrations of
ammonium hydroxide in 0.1 M KCl. The inset to Fig. 5 shows
the calibration curve for NH4OH analysis.

P.C. Pandey, G. Singh / Talanta 55 (2001) 773782

779

sol gel glass layer (urea biosensor-2). The resulting urea biosensor-1 and biosensor-2 responded
nicely. Fig. 7a shows the typical response of the
urea biosensor-1 on the addition of increasing
concentration of urea whereas Fig. 7b shows the
typical response of urea biosensor-2. The results

Fig. 6. The plot of potentiometric response versus pH of

polymer modified electrode.

3.3. Application of new pH sensor in the

construction of the solid-state urea biosensor
We first investigated the response of the sensor
in various buffer of known pH in open-circuit
mode by immersing the pH sensor in different
buffer solutions. The buffer used were 1 mM HCl
(pH 3.0), tris acetate buffer (pH 4 5), phosphate
buffer (pH 6 8) and borate buffer (pH 910).
The result on potentiometric response versus pH
is shown in Fig. 6. There is good linear relation
between pH and potentiometric response. The
slope of the sensor is calculated to be  86 mV
per pH unit. The slope of potentiometric response
is greater than those of glass electrode (59 mV per
pH unit) making the present sensor superior to
that of glass electrode. The super-Nernstian response of the polyaniline-modified pH sensor is
possibly related to non-equilibrium protonation/
de-protonation of nitrogen present in polymer
chain. However, deeper insight justifying proper
reasons for super-Nernstian response is still under
investigation and is on-line on the mechanistic
approach of the polymer chain in non-aqueous
media.
The new pH sensor has been used to develop
urea biosensor by modifying the polymer electrode with immobilised urease. Two protocols for
urease modification of polymer-modified electrode
were adopted. The protocol-1 was based on the
use of PVA matrix (urea biosensor-1) and protocol-2 was based on the use of organically modified

Fig. 7. (a) Typical potentiometric response of new urea biosensor-1 made from immobilised urease in PVA matrix on the
additions of increasing concentrations of urea in 1 mM Tris
HCl buffer pH 7.0. The inset to Fig. 7a shows calibration
curve for urea analysis. (b) Typical potentiometric response of
new urea biosensor-2 made from sandwiched urease within
ormosil on the additions of increasing concentrations of urea
in 1 mM Tris HCl buffer pH 7.0. The inset to Fig. 7b shows
calibration curve for urea analysis.

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P.C. Pandey, G. Singh / Talanta 55 (2001) 773782

on urea sensing is much better than those reported earlier [5,18]. The maximum response is
found to be 160 mV with lowest detection
limit of 20 mM urea. The insets to Fig. 7a and
b shows the plot of potentiometric response versus log of urea concentrations. The response of
urea biosensor-2 was found relatively better as
compared with that of urea biosensor-1, which
may be possibly due to relatively high concentration and better stability of urease on polymer-modified electrode. Since urease was
sandwiched by organically modified solgel
glass as compared with that of urease stabilisation within PVA matrix. The latter immobilisation protocol caused leaching out of urease from
PVA matrix.
The reproducibility of the present urea biosensor was found to be dependent on the stability
of urease within immobilisation matrix. The reproducibility of the present urea biosensor based
on sol-gel glass was found to be excellent retaining \95% initial activity after 2 months (five
operations a day) when stored at 4 C in dry
condition.
The application of new urea biosensor was
examined to analyse serum urea and urea in
milk. In serum samples, the urease contents are
found in accordance close to the values reported
by standard clinical method based on spectrophotometric method. The urea in milk was
determined followed by addition of known
amount of urea in milk. The results recorded
from the urea biosensor showed close relation to
the concentration of added urea. The added
urea concentration in milk was 10 mM and the
detected urea concentration based on potentiometric response was found to be 10.2 mM.

Table 1
Data on temperature dependence of urea biosensor-1
Temperature
(C)

Response of biosensor on the addition of

same concentration of urea (mV)

20
30
40
50

90
102
120
129

increase in potentiometric response on increasing

the temperature up to 50 C. The increase in
potentiometric response of urea biosensor on the
addition of urea was due to increase in urease
activity at relatively higher temperature. After
50 C, the enzyme got denatured and resulted
decrease in potentiometric response.

3.5. Potentiometric measurements in non-aqueous

medium
The polymer-modified electrode was tested for
pH sensing in acetonitrile containing 0.1 M
TPB. The same solution was used as reference
filling solution for Ag/AgCl reference electrode.

3.4. Effects of potential interference on the

response of new biosensor
The effect of temperature on the response of
urea sensor was examined. The electrochemical
cell was thermostated at desired temperature.
The potentiometric responses before and after
urea addition were recorded. Table 1 shows the
response of urea biosensor-1 at three different
temperatures; 20, 30 and 40 C. There was an

Fig. 8. Typical potentiometric response of polymer modified

electrode on the additions of increasing concentrations of
acetic acid in acetonitrile containing 0.1 M tetraphenylborate.
The inset to Fig. 8 shows the calibration curve for acetic acid
analysis.

P.C. Pandey, G. Singh / Talanta 55 (2001) 773782

We tested the detection of acetic acid. Fig. 8

shows the typical response curve for acetic acid
detection. The nature of potentiometric signal
on the addition of acetic acid in acetonitrile was
found to be different as recorded for the same
in aqueous medium which resulted a S-shaped
curve in aqueous medium where as the same has
different shape in non-aqueous medium. The initial response was found to be very low and subsequently increases on increasing acetic acid
concentration (Fig. 8). In non-aqueous medium,
the potentiometric response as a function of acetic acid concentration might not have direct relationship on hydrogen-ion activity or pH,
which may cause variation in nature of acetic
acid sensing in acetonitrile. The inset to Fig. 8
shows the calibration curve for acetic acid analysis. The slope at low concentration of acetic
acid was found less and further the same became high on increasing acetic acid concentration. The non-linear shape of calibration curve
was not detected at high acetic acid concentration as was observed in aqueous medium under
similar condition.
It is again important to discuss the expenses
involved in the construction of simple polymer
modified electrode for commercial viability. The
preparation protocol justified the inexpensive design as compared with earlier reported pH
transducers, which is needless to quote.
We developed potentiometric urea and acetylcholine biosensor using present pH transducer.
The biosensor was developed encapsulating urease or acetylcholinesterase within ormosil. The
results on acetylcholine sensing has been observed quite impressive and reported elsewhere.
We also tried to immobilise lipoxygenase on the
present polymer modified electrode again using
ormosil. Since lipoxygenase catalysed reaction
again generated oeleic acid while using linoleic
acid as substrate, we observed potentiometric response in the presence and absence of lipoxygenase. The results are still underway to analyse
the contribution of oeleic acid and linoleic acid
sensing kinetically. The researches are still ongoing to study the mechanistic approach of polymer preparation in non-aqueous medium
containing TPB.

781

4. Conclusion
In summary, we report herein a novel solidstate pH sensor based on tetraphenylborate
doped polyaniline synthesised in non-aqueous
medium. The application of organic polymer obtained by electropolymerisation of aniline in dry
acetonitrile containing 0.5 M tetraphenylborate
perfectly suitable for pH sensing in both nonaqueous and aqueous mediums. The typical
analysis of acid and base in aqueous and in
non-aqueous is reported. The new sensor is
highly stable as compared with other reported
sensor of commercial interest. The present pH
transducer has been used in the construction of
urea biosensor with relatively better sensitivity
and stability. The performance of pH transducer, urea biosensor is reported.

Acknowledgements
The authors are thankful to UGC New Delhi
for financial assistance Govind Singh is thankful
to CSIR for the award SRF.

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