Sensors and Actuators B 228 (2016) 278–286
Contents lists available at ScienceDirect
Sensors and Actuators B: Chemical
jo u r nal homep age: www.elsevier.com/locate/snb
An effective surface design based on a conjugated polymer and silver
nanowires for the detection of paraoxon in tap water and milk
Janset Turan
a
, Melis Kesik
a
, Saniye Soylemez
a,1
, Seza Goker
a
, Sahin Coskun
c
,
Husnu Emrah Unalan
c,e
, Levent Toppare
a,b,d,e,∗
a
Department of Chemistry, Middle East Technical University, Ankara 06800, Turkey
b
Department of Biotechnology, Middle East Technical University, Ankara 06800, Turkey
c
Department of Metallurgical and Materials Engineering, Middle East Technical University, Ankara 06800, Turkey
d
Department of Polymer Science and Technology, Middle East Technical University, Ankara 06800, Turkey
e
The Center for Solar Energy Research and Application (GUNAM), Middle East Technical University, Ankara 06800, Turkey
a r t i c l e i n f o
Article history:
Received 3 November 2015
Received in revised form
22 December 2015
Accepted 9 January 2016
Available online 13 January 2016
Keywords:
Amperometric biosensor
Conducting polymer
Silver nanowire
Pesticide biosensor
Butyrylcholinesterase
a b s t r a c t
In this study, a novel approach for the fabrication of a biosensor utilizing a conducting polymer
and silver nanowires is reported. To obtain immobilization platform for butyrylcholinesterase (BChE),
a graphite electrode was modified with the poly(5,6-bis(octyloxy)-4,7-di(thieno[3][3,2-b]thiophen-2-
yl)benzo[c][1,2,5]oxoadiazole) (PTTBO) which has a hydrophobic alkyl chain as the pendant group
providing hydrophobic nature to the matrix. Since biomolecules contain both hydrophobic and
hydrophilic parts in their structure, alkyl chains interact with the proteins which provide an enhanced
stability. Biosensor performance was improved through the deposition of silver nanowires on the polymer
coated surfaces which enhances the charge transfer rate. This enabled the development of rapid, highly
sensitive and stable amperometric sensors for the quantitative determination of organophosphorus pes-
ticide; paraoxon. Fabricated biosensor showed two linear ranges between 0.5–8 M and 10–120 M
with a low detection limit of 0.212 M when butyryl thiocholine iodide is used as the substrate. Surface
modifications were monitored by scanning electron microscope (SEM) and cyclic voltammetry (CV) tech-
niques. Under optimal operational parameters, fabricated sensors were tested for paraoxon detection in
milk and tap water based on the inhibition of the enzyme molecules, where recovery tests proved the
applicability of the designed system.
© 2016 Elsevier B.V. All rights reserved.
1. Introduction
Environmental monitoring and food control are the two main
concerns in many research fields due to the excessive use of pes-
ticides in agriculture, industry and chemical warfare [1]. Among
the pesticides, organophosphates and carbamic pesticides are the
most commonly used ones in agriculture as insecticides in order
to fight pests and to increase the yield. Unfortunately, toxicity of
these compounds causes serious health defects on mammalians
due to their inhibitory effect on cholinesterase enzyme (ChE) [2].
∗
Corresponding author at: Middle East Technical University, Department of
Chemistry, Ankara 06800, Turkey. Fax: +90 3122103200.
E-mail addresses: janset.trn@gmail.com (J. Turan),
kesik.melis@gmail.com (M. Kesik), saniyesoylemez@gmail.com
(S. Soylemez), sezagoker@gmail.com (S. Goker), sacoskun@metu.edu.tr (S. Coskun),
unalan@metu.edu.tr (H.E. Unalan), toppare@metu.edu.tr (L. Toppare).
1
On leave from Ordu University.
Blockage of the active sides of ChE by pesticides can result in distur-
bance of normal neuronal function, which leads to immunological
diseases, nerve disorders and eventually death [3]. Since contam-
ination of agricultural products and aquatic systems cause these
lethal effects, the need for pesticide detection gains high priority.
Chromatographic methods, such as high performance liquid chro-
matography (HPLC), gas chromatography (GC), mass-spectrometry
(MS) among others have been employed for monitoring pesticides
in contaminated water and food products [4–6]. Such analytical
methods provide very sensitive and selective detection. Never-
theless, they have also several drawbacks as they require long
analysis time, complicated pretreatment methods, qualified opera-
tors and intricate equipments [7]. To minimize these complications,
cholinesterase enzymes based bioanalytical systems integrated
with amperometric, potentiometric and optical methods have been
employed over the last few years [8–13]. These analytical systems
not only provide fast and highly sensitive detection but also are
potentially applicable for use in field. Recently, enzyme inhibi-
http://dx.doi.org/10.1016/j.snb.2016.01.034
0925-4005/© 2016 Elsevier B.V. All rights reserved.