Talanta 79 (2009) 1197–1203
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Talanta
journal homepage: www.elsevier.com/locate/talanta
A novel high selective and sensitive para-nitrophenol voltammetric sensor, based
on a molecularly imprinted polymer–carbon paste electrode
Taher Alizadeh
a,∗
, Mohammad Reza Ganjali
b,c
, Parviz Norouzi
b,c
, Mashallah Zare
b
, Ali Zeraatkar
b
a
Department of Applied Chemistry, Faculty of Science, University of Mohaghegh Ardabili, Ardabil, Iran
b
Center of Excellence in Electrochemistry, Faculty of Chemistry, University of Tehran, Tehran, Iran
c
Endocrinology & Metabolism Research Center, Medical Sciences/University of Tehran, Tehran, Iran
article info
Article history:
Received 12 January 2009
Received in revised form 20 February 2009
Accepted 21 February 2009
Available online 9 March 2009
Keywords:
Para-nitrophenol
Molecularly imprinted polymer
Voltammetric sensor
Carbon paste electrode
abstract
By using a molecularly imprinted polymer (MIP) as a recognition element, the design and construction
of a high selective voltammetric sensor for para-nitrophenol was formed. Para-nitrophenol selective MIP
and a non-imprinted polymer (NIP) were synthesized, and then used for carbon paste (CP) electrode
preparation. The MIP–CP electrode showed greater recognition ability in comparison to the NIP–CP. It
was shown that electrode washing after para-nitrophenol extraction led to enhanced selectivity, without
noticeably decreasing the sensitivity. Some parameters affecting sensor response were optimized and a
calibration curve was plotted. A dynamic linear range of 8 × 10
-9
to 5 × 10
-6
mol L
-1
was obtained. The
detection limit of the sensor was calculated as 3 × 10
-9
mol L
-1
. Thus, this sensor was used successfully
for the para-nitrophenol determination in different water samples.
© 2009 Elsevier B.V. All rights reserved.
1. Introduction
Phenol compounds such as nitrophenols are amongst the
category of serious environmental contaminants, and their deter-
mination in environmental samples has been of high interest due
to their toxic effects on humans, animals and plants [1]. Nitroaro-
matic compounds can be formed by photochemical atmospheric
reactions owing to the presence of nitrogen oxides in industrial
and automotive emission gases. They are also widely used in
the production of pesticides, paints and explosive materials [2,3].
Nitroaromatic compounds are considered by the United States Envi-
ronmental Protection Agency as main pollutants, because they are
toxic to human health [4]. In particular, para-nitrophenol is a toxic
hydrolysis product of the insecticides parathion and paraoxon, and
also exists in wastewater from industries such as refineries. Detox-
ification of water contaminated with nitroaromatic compounds is
usually a very difficult process since the presence of a nitro-group
on the aromatic compound. This confers a strong chemical stabil-
ity and resistance of microbial degradation [5]. The detection of
para-nitrophenol is important for protecting water resources and
food supplies in the defense against terrorist activity, and for mon-
itoring detoxification processes [6]. Therefore, there are growing
demands for portable devices for reliable on-site monitoring of
para-nitrophenol compounds.
∗
Corresponding author. Tel.: +98 451 5514702; fax: +98 451 5514701.
E-mail address: taa 55@yahoo.com (T. Alizadeh).
Some laboratory-based analytical methods for determin-
ing para-nitrophenol compounds such as; gas and liquid
chromatography [7–13], UV–vis spectrophotometry [12,13] and
spectrofluorimetry [14] have been reported. The use of enzyme-
linked immunosorbent assay has also been accounted for [15].
However, for the majority of these methods, some sample pre-
treatment involving separation, extraction and adsorption is
generally necessary. These can be time-consuming and com-
plex.
Electrochemical methods, such as differential pulse polarog-
raphy, anodic stripping voltammetry and differential pulse
voltammetry, have been widely applied for the determination of
pharmaceuticals, dyes, insecticides, pesticides and inorganic ions
[16–19].
Modified electrodes are being used frequently in the voltammet-
ric determination of organic compounds because of their efficiency
and the selectivity that can be obtained by varying the modi-
fier. In recent years, chemically modified electrodes were used for
the voltammetric quantification of various organic and inorganic
species after their accumulation [20–22]. Multitudes of modifying
agents were used either as coatings on solid electrode surfaces, or
dispersed within a conductive matrix. Some modified electrodes
have been reported such as: a glass carbon electrode impregnated
with a lithium tetracyanoethylenide (LiTCNE) [23], and a sodium
montmorillonite-anthraquinone chemically modified glass carbon
electrode [6], for the determination of para-nitrophenol. These
modifiers have advantages—stability for a long duration of time
and simplicity in preparation. However, they suffer from a main
0039-9140/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.talanta.2009.02.051