Development of an imprinted polymeric sensor with dual sensing
property for trace level estimation of zinc and arginine
Ekta Roy
a
, Santanu Patra
a
, Rashmi Madhuri
a,
⁎, Prashant K. Sharma
b
a
Department of Applied Chemistry, Indian School of Mines, Dhanbad, Jharkhand 826 004, India
b
Department of Applied Physics, Indian School of Mines, Dhanbad, Jharkhand 826 004, India
abstract article info
Article history:
Received 28 July 2014
Received in revised form 28 October 2014
Accepted 17 December 2014
Available online 19 December 2014
Keywords:
Multi-template imprinting
Zn
2+
Arginine
Biocompatible
Multi-walled carbon nanotubes
Electrochemical sensor
Using virtuousness of multi-template imprinting and selectivity of single-template imprinting, for the first time,
we have prepared an imprinted polymer matrix that can detect two target analyte viz., Zn
2+
and arginine in sin-
gle motif. For the preparation of imprinted polymer network, a new monomer {2-acrylamido-4-(methylthio)
butanoic acid} was synthesized, which gives a biocompatible polymer network. Herein, the synthesized
imprinted polymer mixed with multi-walled carbon nanotubes was immobilized onto the surface of platinum
electrode to develop an electrochemical sensor for quantitative recognition of Zn
2+
and arginine using differen-
tial pulse voltammetry. Cyclic voltammetry, electrochemical impedance spectroscopy, and chronocoulometric
analysis were also performed to study the kinetics of zinc–arginine complex. Under the optimal conditions the
linear range of the calibration curve for Zn
2+
and arginine was 0.04–310.0 ng mL
-1
and 0.04–235.0 ng mL
-1
,
with the detection limit of 18.0 and 15.0 pg mL
-1
. The sensor has been successfully applied to the determination
of Zn
2+
and arginine in water, food, and pharmaceutical samples and achieved high sensitivity and selectivity.
© 2014 Elsevier B.V. All rights reserved.
1. Introduction
Molecular imprinting technology offers the possibility of producing
ligand selective recognition sites in synthetic polymers. Generally, syn-
thesis of molecularly imprinted polymers (MIPs) were carried out by
polymerization of one or more than one monomers in the presence of
a template and cross-linker, followed by removal of the template to
leave a binding cavity with selectivity to the template molecule [1]. If,
a single template molecule is used to create the specific binding site in
the polymer matrix is called as single template imprinting. However,
the imprinting process is not limited to a single template, and several
compounds can be imprinted simultaneously i.e., known as multi-
template imprinting [2,3]. Multi-template imprinting have several ad-
vantage over single template imprinting like, several different classes
of compounds can be extracted, separated, assayed, detected, or other-
wise analyzed at a single time. However, several disadvantages are also
available resulting in less-popularity of multi-imprinting viz., template
leakage and poor binding capability [4]. Keeping together the virtuous-
ness of multi-template imprinting and specificity of single template
imprinting, for the first time, we have reported a single template-
imprinted polymer, which can able to detect two target molecules si-
multaneously. Herein, zinc–arginine complex was used as template
molecule, but the complex-imprinted polymer (CIP) can detect both
zinc and arginine at ultra trace level.
Zinc metal ion is an antioxidant and active element in the cons-
titution of approximately sixty enzymes, has an important role in:
maintaining vision, protein metabolism, activity of the pancreas, stimu-
lation of assimilation of vitamins, training leukocytes, immune activa-
tion, favoring nucleic acid synthesis, and repair processes [5,6]. Zinc
can be considered as one of the most important trace elements because
of its involvement in the construction and manufacturing of cellular
mechanisms. Along with its good behavior, zinc is also a very popular el-
ement owed to its hazardous effects, which affect the environment as
well as human life [7]. Recently, the use of toxic metals such as zinc,
nickel, lead and mercury has been prohibited in many industrial fields
as environmental protective regulations (viz., Restriction of hazardous
substances and End of Life Vehicle) and extensively applied worldwide.
As zinc is one of widely used metals and very frequently found in water
(waste water, drinking water, and tap water), we have taken it as a one
of target analyte. Although, the direct analysis of trace elements in food
samples or water sample is still a difficult task, not only because of the
low concentration of trace elements, but also because of the complex
matrix which interferes with their determination. Thus, the variety of
pre-treatment techniques, such as solid phase extraction [8], solvent ex-
traction and co-precipitation [9] prior to instrumental measurements
has been exploited to achieve accurate and reliable results. Among the
various methods, atomic absorption spectrometry (AAS) [10], atomic
emission spectrometry (AES) [11] and mass spectrometry (MS) [12]
are commonly used for the determination of heavy metal ions. Howev-
er, these techniques have some disadvantages, such as complicated op-
eration, high cost of maintenance, expensive apparatus, and require
Materials Science and Engineering C 49 (2015) 25–33
⁎ Corresponding author.
E-mail address: rshmmadhuri@gmail.com (R. Madhuri).
http://dx.doi.org/10.1016/j.msec.2014.12.066
0928-4931/© 2014 Elsevier B.V. All rights reserved.
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