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Chemical Papers
https://doi.org/10.1007/s11696-018-0523-6
ORIGINAL PAPER
Synthesis, characterization and using a new terpyridine moiety‑based
ion‑imprinted polymer nanoparticle: sub‑nanomolar detection
of Pb(II) in biological and water samples
Mojtaba Shamsipur
1
· Leila Samandari
1
· Abbas Besharati‑Seidani
2
· Afshin Pashabadi
1
Received: 12 February 2018 / Accepted: 29 May 2018
© Institute of Chemistry, Slovak Academy of Sciences 2018
Abstract
A highly selective lead-imprinted polymer was synthesized via a thermal precipitation polymerization technique based on a
terpyridine-based ligand as the complexing agent. The synthesized polymer was successfully incorporated in a graphite paste
electrode (GPE) as the recognition element for lead ion (Pb
2+
). Differential pulse anodic stripping voltammetry (DPASV)
technique was used to transduce the binding events at the modified electrode. The imprinted polymer nanoparticles (IP-NPs)
were synthesized by precipitation polymerization of ethylene glycol dimethacrylate as the cross-linker, 2,2′-azobisisobu-
tyronitrile as the free radical initiator and 2,2′:6′,6″-terpyridine (terpy) as the recognition element. The sensing procedure is
based on the accumulation of lead ions at − 1.0 V vs. Ag/AgCl. Afterward, the DPV was recorded by the sweeping potential
in a positive direction to oxidize the accumulated ions, leading to the appearance of a significant anodic peak. The constructed
IIP–GPE revealed a linear response toward Pb
2+
over the concentration range from 0.4 to 10 nM (with the sensitivity of
693.95 nA nM
−1
cm
−2
) and 10 nM to 1.0 µM (with the sensitivity of 580.25 µA µM
−1
cm
−2
). The limit of detection (LOD)
was evaluated to be 0.11 nM (for S/N = 3). The accuracy of the sensor was explored by analysis of a quality control mate-
rial (QCMs, Seronorm™ urine REF NO 1011645) and different water samples. Selectivity studies showed no particular
interference for detection of Pb(II).
Keywords Terpyridine · Ion-imprinted polymer · Graphite paste electrode · Stripping voltammetry · Lead ions
Introduction
The contamination of the environment due to its adverse
effects on ecosystems and human health is one of the main
problems facing humanity today. Heavy metals, including
lead (Pb(II)), are one of the most important environmental
pollutants which gradually accumulate in plants, animals
and humans. Lead has also strong chemical toxic effects on
organs such as heart, bones, nervous, immune, reproductive,
renal, and gastrointestinal systems, even in the presence of
low concentration (Kemper and Sommer 2002). Young chil-
dren are more susceptible to lead exposure than adults due to
the differences in iron metabolite genes and the higher rate
of lead absorption by intestines and its persistence in their
body (Hung et al. 2010).
Based on the World Health Organization (WHO) guide-
line, the safe level of Pb
2+
in potable water is approximately
48 nM (WHO 2011). Due to the lead accumulation capabil-
ity, it is necessary to identify trace levels of Pb in environ-
ment sources and biological samples before it reaches the
risk level.
For this purpose, several analytical methods have been
extended especially by means of a wide range of spectro-
metric techniques, such as X-ray fluorescence spectrometry
(Eksperiandova et al. 2002), atomic absorption spectrom-
etry (Smith et al. 1979), inductively coupled plasma mass
spectrometry (Jenner et al. 1990), graphite furnace atomic
absorption (Behbahani et al. 2015; Shamsipur et al. 2014),
and hydride generation atomic absorption spectrometry
(Korkmaz et al. 2002). These methods have the advantages
of high sensitivity and selectivity, but still have the sub-
stantial weakness, such as the expensive cost, professional
* Mojtaba Shamsipur
mshamsipur@yahoo.com
1
Department of Chemistry, Razi University, Kermanshah,
Iran
2
Department of Chemistry, Malek-Ashtar University
of Technology, Tehran, Iran
@Phil_Robichaud
@deepthiw
@JoseServera