Talanta 84 (2011) 905–912
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Talanta
journal homepage: www.elsevier.com/locate/talanta
A novel high selective and sensitive metronidazole voltammetric sensor based on
a molecularly imprinted polymer-carbon paste electrode
Mohammad Bagher Gholivand
∗
, Maryam Torkashvand
Department of Analytical Chemistry, Faculty of Chemistry, Razi University, Kermanshah, Iran
article info
Article history:
Received 6 December 2010
Received in revised form 10 February 2011
Accepted 16 February 2011
Available online 22 February 2011
Keywords:
Metronidazole
Molecularly imprinted polymer
Cathodic stripping voltammetry
Carbon paste
abstract
The design and construction of a highly selective voltammetric sensor for metronidazole by using a molec-
ularly imprinted polymer (MIP) as recognition element were introduced. A metronidazole selective MIP
and a nonimprinted polymer (NIP) were synthesized and then incorporated in the carbon paste electrodes
(CPEs). The sensor was applied for metronidazole determination using cathodic stripping voltammetric
method. The MIP–CP electrode showed very high recognition ability in comparison to NIP-CPE. Some
parameters affecting the sensor response were optimized and then the calibration curve was plotted.
Two dynamic linear ranges of 5.64 × 10
−5
to 2.63 × 10
−3
mg L
−1
and 2.63 × 10
−3
to 7.69 × 10
−2
mg L
−1
were obtained. The detection limit of the sensor was calculated as 3.59 × 10
−5
mg L
−1
. This sensor was
used successfully for metronidazole determination in biological fluids.
© 2011 Elsevier B.V. All rights reserved.
1. Introduction
Metronidazole is a nitroimidazole derivative and has been
widely used for the treatment of protozoal diseases including
trichomoniasis and giardiasis [1]. This drug is effective against
trichomonas, Vincent’s organisms, and anaerobic bacteria. Veteri-
narians also use metronidazole to treat bacterial infections as well
as giardia in dogs and cats [2]. Metronidazole [3] contains a nitro
group which is the electrochemically active reducible center. In
the absence of oxygen the reduction process for nitroimidazoles
is similar to that for nitrobenzene [4].
Several methods have been reported for determination
of metronidazole which include potentiometric [5,6], polaro-
graphic [7,8], gas chromatography [9,10], supercritical fluid
chromatography [11], thin layer chromatography (TLC) [12], high-
performance liquid chromatography (HPLC) [13–16], voltammetric
[17], derivative spectrophotometry [18–20], luminescence [21],
and spectrophotometry [22–24]. However, these methods have
some drawbacks such as time consuming, narrow range of determi-
nation, requirement of heating or extraction, the use of nonaqueous
systems, stability of the colored product formed, etc. [25]. Hence,
it is of primary importance to develop an alternative method for
metronidazole determination with a high degree of selectivity and
sensitivity.
Chemically modified carbon paste electrodes (CMCPE) have
been continued to be of a major concern during the past decade.
∗
Corresponding author. Tel.: +98 831 4274557; fax: +98 831 4274559.
E-mail address: mbgholivand@yahoo.com (M.B. Gholivand).
Furthermore a relatively large number of electrochemical research
has been devoted to the development and applications of different
types of CMCPE [26–31]. Modification of carbon paste electrodes
with suitable materials facilitates the electrochemical reactions of
the redox compounds to proceed without hindrance [32,33]. This
phenomenon generally results increasing in selectivity and sensi-
tivity of the determinations [34–36].
Molecularly imprinted polymers (MIPs) are extensively cross-
linked polymers containing specific recognition sites with a
predetermined selectivity for analytes. The procedure for syn-
thesizing an MIP is based on the polymerization of a functional
monomer and a cross-linking agent in the presence of a template.
When the imprinted molecule is removed, the imprinted polymer
with a high affinity for the template molecule is obtained. This affin-
ity is due to the shape and the arrangement of the functional of the
monomer units [37]. The MIPs are used as antibody like materials
for high selectivity and sensitivity, chemical inertness, long-term
stability, availability in large quantities, and insolubility in water
and most organic solvents [38,39]. MIPs are promising materials
continually being used in sensor fields such as recognition elements
or modifying agents (instead of other commonly used modifiers).
The application of MIPs in electrochemistry is rather recent and
was directed to combine their intrinsic properties to selected elec-
trochemical reactions, in order to improve the response of the
electrode [40,41].
This study was led to the development of a new MIP modified
electrode for the determination of metronidazole with improved
qualities such as: simplicity of electrode preparation, a wider linear
range, lower detection limit (DL), higher selectivity and more stabil-
ity of the used modifier. The procedure was based on the reduction
0039-9140/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.talanta.2011.02.022