Sensors and Actuators B 245 (2017) 605–614
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Sensors and Actuators B: Chemical
jo ur nal home page: www.elsevier.com/locate/snb
Development of a highly selective and sensitive electrochemical
sensor for Bi
3+
determination based on nano-structured
bismuth-imprinted polymer modified carbon/carbon nanotube paste
electrode
Taher Alizadeh
a,∗
, Negin Hamidi
a
, Mohamad Reza Ganjali
a,b
, Parviz Nourozi
a
a
Department of Analytical Chemistry, Faculty of Chemistry, University College of Science, University of Tehran, P.O. Box 14155-6455, Tehran, Iran
b
Biosensor Research Center, Endocrinology & Metabolism Molecular-Cellular Sciences Institute, Tehran University of Medical Sciences, Tehran, Iran
a r t i c l e i n f o
Article history:
Received 13 October 2016
Received in revised form 20 January 2017
Accepted 2 February 2017
Available online 3 February 2017
Keywords:
Bismuth
Ion-imprinted polymer
Carbon nanotube
Carbon paste
Voltammetric sensor
a b s t r a c t
A new nano-structured bismuth(III)-imprinted polymer was prepared by copolymerization of Bi(III)-
methylene succinate complex and ethylene glycol dimethacrylate in acetonitrile via precipitation
polymerization technique. The polymeric nanoparticles were then used as the Bi
3+
selective modifier
of a carbon/carbon nanotube paste electrode. Bismuth ions were accumulated on the surface of the
electrode, immersed in the Bi
3+
solution for a definite time. Then, the anodic striping differential pulse
voltammetric signal of the modified electrode was recorded as analytical signal which was significantly
higher than that recorded by the non-imprinted polymer based electrode, at the same experimental con-
ditions. Compared to the previously reported carbon paste electrodes, this sensor was more selective,
regarding potential interfering species of Cu
2+
and Ag
+
. The electrode exhibited a dynamic linear response
range of 0.2–2 mol L
-1
and detection limit of 8.9 nmol L
-1
for Bi
3+
measurement. The sensitivity of the
sensor was 112.25 A M
-1
, indicating an excellent sensitivity of the developed sensor. The sensor was
successfully applied for the electrochemical determination of Bi
3+
ions in environmental, pharmaceutical
and biological samples.
© 2017 Elsevier B.V. All rights reserved.
1. Introduction
Bismuth and its compounds are presently employed in the fab-
rication of semiconductors and alloys. Bismuth compounds have
important applications in pharmaceutical preparations. They are
employed as antibacterial, anti-HIV and radiotherapeutic agents.
Furthermore, bismuth compounds are widely used in the treatment
of syphilis, helicobacter pylori induced gastritis and dermatologi-
cal disorders. Bismuth is also utilized for the preparation of creams
and hair dyes [1–3]. However, some toxic effects in humans such
as nephropathy, osteoarthropathy, hepatitis and neuropathology
have been assigned to bismuth compounds [2].
The development of selective separation or determination
methods for bismuth is a challenge because of low level concentra-
tions of bismuth in natural samples and strong interference effect
of sample matrix on its determination [1].
∗
Corresponding author.
E-mail addresses: talizadeh@ut.ac.ir, taa 55@yahoo.com (T. Alizadeh).
Several instrumental methods including coupled plasma atomic
emission spectrometry (ICP-AES [4], ICP mass spectrometry (ICP-
MS) [5], atomic absorption spectrometry (AAS) [6] and atomic
fluorescence spectrometry (AFS) [7] have already been introduced
for the measurement of bismuth. These techniques are sensitive
and selective; but, they require expensive instruments and time
consuming sample pretreatment [2].
Generally, electrochemical determination of Bi
3+
is complex due
to the strong tendency of bismuth salts to hydrolysis even at acidic
pH conditions. Consequently, very acidic medium must be used
to avoid hydrolysis of Bi(III) [8]. In spite of this, electrochemi-
cal methods such as potentiometric stripping analysis (PSA) [9],
anodic stripping voltammetry (ASV) [10–13] and cathodic stripping
voltammetry (CSV) [14,15] have been proposed for the determina-
tion of bismuth. Such described methods are comparatively simple
and provide rapid response and high sensitivity; but, they all utilize
toxic mercury, as working electrode [2].
Carbon paste electrodes (CPEs) have been extensively used
for the electrochemical monitoring of metal ions, because of
http://dx.doi.org/10.1016/j.snb.2017.02.024
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