Biosensors and Bioelectronics 71 (2015) 137–142

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Biosensors and Bioelectronics

journal homepage: www.elsevier.com/locate/bios

Electrochemical sensor for paracetamol recognition and detection

based on catalytic and imprinted composite film
Ying Teng a,b, Limei Fan a,b, Yunlong Dai a,b, Min Zhong a,b, Xiaojing Lu a,b, Xianwen Kan a,b,n
a
College of Chemistry and Materials Science, Anhui Normal University, Wuhu 241000, PR China
b
The Key Laboratory of Functional Molecular Solids, Ministry of Education, Anhui Laboratory of Molecule-Based Materials, Anhui Key Laboratory of Chemo-
Biosensing, Anhui Key Laboratory of Functional Molecular Solids, PR China

art ic l e i nf o a b s t r a c t

Article history: A new strategy for a composite film based electrochemical sensor was developed in this work. A layer of
Received 18 January 2015 conductive film of poly(p-aminobenzene sulfonic acid) (pABSA) was electropolymerized onto glassy
Received in revised form carbon electrode surface and exhibited a high electrocatalytic active for paracetamol (PR) redox. The
10 April 2015
subsequent formation of a layer of molecular imprinted polymer (MIP) film on pABSA modified electrode
Accepted 13 April 2015
endowed the sensor with plentiful imprinted cavities for PR specific adsorption. The advantages of the
Available online 14 April 2015
composite film made the prepared sensor display high sensitivity and good selectivity for PR detection
Keywords: and recognition. Under the optimal conditions, the sensor could recognize PR from its interferents. A
Electrochemical sensor linear ranging from 5.0
10  8 to 1.0
10  4 mol/L for PR detection was obtained with a detection limit of
Conductive polymer
4.3
10  8 mol/L. The sensor has been applied to analyze PR in tablets and human urine samples with
Molecular imprinted polymer
satisfactory results. The simple, low cost, and efficient strategy reported here can be further used to
Paracetamol
Electrocatalysis prepare electrochemical sensors for other compounds recognition and detection.
& 2015 Elsevier B.V. All rights reserved.

1. Introduction 2014a; Li et al., 2012a,b). Even though the conductive polymers,

As a kind of synthetic material, molecular imprinting polymer
(MIP) simulates the behavior of natural antibodies and exhibits
greater stability than its natural counterparts, resulting in its wide
applications in the field of chromatography separation, solid phase
extraction, drug controlled release, and electrochemical sensor (Jin
et al., 2013; Rossetti et al., 2014; Zeng et al., 2013). Traditional
synthetic methods, such as UV and chemically initiated poly-
merizations, have been investigated and applied for lots of small
molecules and biomacromolecules recognition (Wulff et al., 1973;
Vlatkis et al., 1993). In electrochemical sensors, electro-
polymerization methods for MIP preparation exhibit many ad-
vantages, such as simple preparation procedures, easy control of
the thickness of the film, and uniform polymer distribution on
electrode surface. The modified MIP film on electrode surface acts
as a molecular recognition element to improve the selectivity of
the sensor due to its specific adsorption capacity. Generally, the
electropolymerized MIP films are non electroactive, resulting in
the lack of direct path for the conduction of electrons from the
active sites to electrode (Whitcombe et al., 2011; Wang et al.,
n
Corresponding author at: College of Chemistry and Materials Science, Anhui
Normal University, Wuhu 241000, PR China.. Fax: þ 86 553 3869303.
E-mail address: kanxw@mail.ahnu.edu.cn (X. Kan).
such as polypyrrole and polyaniline, were involved, the over-
oxidation procedure was implemented before the determination
also to restrain the non specific adsorption (Turco et al., 2015; Kan
et al., 2012). Thus, the sensitivity of the MIP based electrochemical
sensors would be seriously limited.
Due to the high surface-to-volume ratio, enhancement of the
conductivity and acceleration of the electron transfer, various na-
nomaterials have been introduced into the MIP based electro-
chemical sensors preparation. Graphene, carbon nanotubes, gold
nanoparticles et al. have been used to fabricate effective sensing
platforms for electrochemical sensors. These nanomaterials based
MIP electrochemical sensors exhibited improved sensitivity for
template molecules detection (Riskin et al., 2008; Li et al., 2012a,b;
Cai et al., 2010; Xie et al., 2010; Flavin and Resmini, 2009). Besides
these nanomaterials, conductive polymers have been widely used
in electrochemical sensors since they also can accelerate the
electron transfer at the electrode–solution interface and sig-
nificantly enhance the electrode reaction rate (Kong et al., 2014).
Moreover, the advantages of stable coating on electrode and low
cost make the conductive polymers perfect for electrochemical
sensor preparation to improve the sensitivity in a sense. Yang et al.
reported that a poly(malachite green) film-coated electrode dis-
played high electrocatalytic activity to dopamine (Wang et al.,
2007). Cheng et al. investigated the electrocatalytic oxidation of
cysteine at screen-printed electrode, which was modified with

http://dx.doi.org/10.1016/j.bios.2015.04.037
0956-5663/& 2015 Elsevier B.V. All rights reserved.
138 Y. Teng et al. / Biosensors and Bioelectronics 71 (2015) 137–142
electrogenerated poly(3,4-ethylenediocythiophene) film. The pre-
pared modified polymer film lowered the overpotentials and im-
proved electrochemical behavior of cycteine oxidation (Su and
Cheng, 2008). Thionine was used as a monomer for a poly(thio-
nine) modified electrode preparation. Excellent catalytic activity
and reversibility for the electrochemical redox reaction of both
hydroquinone and catechol were achieved with a really low de-
tection limit (Ahammad et al., 2011).
Among the conductive polymers synthesis, sulfonated poly-
aniline, as the first reported self-doped water-soluble conducting
polyaniline derivative, is of interest because of its high stability
and good conductivity in a broad pH range (Wei et al., 1996). p-
Aminobenzene sulfonic acid (ABSA) is a kind of electroactive
compound and has been successfully electropolymerized to form
poly(p-aminobenzene sulfonic acid) (pABSA) film by many re-
searchers under different conditions. Chen et al. electro-
polymerized a composite of pABSA and flavins on electrode sur-
face, which showed excellent electrocatalytic activity for NADH
redox (Kumar and Chen, 2007). A pABSA film modified electrode
fabricated by electropolymerization showed an electrocatalytic
activity for the oxidation of dopamine and ascorbic acid, resulting
in the simultaneously determination of both compounds (Jin et al.,
2005). It is of no doubt that the excellent conductivity and elec-
trocatalysis of pABSA could provide a platform to facilitate the
conduction of electrons. Hence, the combination of MIP and con-
ductive polymers can be proposed for achieving good recognition
capacity as well as high sensitivity of the electrochemical sensor.
Paracetamol (PR), as an antipyretic/analgesic, is rapidly and
completely metabolized to form inactive metabolites, which
would be eliminated in the urine in body (Markas, 1994). However,
overdosing and the chronic use of PR produces toxic metabolite
accumulation that will cause skin rashes and inflammation of the
pancreas (Shiroma et al., 2012). An electrochemical sensor was
prepared by modifying graphene on glassy carbon electrode
surface for PR detection with a linear range of
1.0
10  7–2.0
10  5 mol/L. A quasi-reversible redox process of
PR at the modified electrode and the significant decrease of over-
potential of PR were attributed to the electrocatalytic activity of
graphene (Kang et al., 2010). A layer of MIP film was reported to be
electropolymerized onto multiwalled carbon nanotubes modified
electrode surface for PR detection and recognition. The sensor not
only recognized PR from its possible interfering substances, but
also sensitively detected PR with a linear range of
2.0
10  7–4.0
10  5 mol/L (Peng et al., 2014). Electrochemical
sensors based on multiwalled carbon nanotubes and dopamine
nanospheres functionalized with gold nanoparticles (Liu et al.,
2014), Pd/graphene oxide nanocomposite (J. Li et al., 2014a, Y. Li
et al., 2014b), nanogolds (Goyal et al., 2005), have been reported
for PR determined with some satisfactory results. These nanoma-
terials used for sensor preparation can improve the sensitivity of
the sensor. Herein, two layers of polymer films were electrpoly-
merized on glassy carbon electrode (GCE) surface successively to
fabricate a novel and facile electrochemical sensor. ABSA was
chosen as a monomer to form the first layer of polymer, providing
a conductive and catalytic platform for PR sensitive detection. And
o-phenylenediamine (OPD) was chosen as a monomer for the
second film preparation in the presence of PR to form MIP, en-
dowing the sensor with good selective recognition capacity to-
ward PR.
2. Experimental
2.1. Chemicals
Commercially available reagents were used without further
purification. p-aminobenzene sulfonic acid (ABSA) and para-
cetamol (PR, 499%) were ordered from Aladdin (Aladdin, China).
o-phenylenediamine (OPD), 4-nitrophenol (4-NP), and ascorbic
acid (AA) were purchased from Sinopharm Chemical Reagent Co.
Ltd. (China). Uric acid (UA), dopamine (DA), and hydroquinone
(HQ) were provided by Sigma (Sigma, USA). All other reagents
were of at least analytical-reagent grade, and double-distilled
deionized water was used for all solutions.
2.2. Apparatus
Electrochemical experiments, such as cyclic voltammetry (CV),
electrochemical impedance spectroscopy (EIS) and differential
pulse voltammetry (DPV) were performed on CHI 660C work-
station (ChenHua Instruments Co., Shanghai, China) with a con-
ventional three-electrode system. A bare or modified glassy carbon
electrode (GCE) was served as a working electrode. A saturated
calomel electrode and a platinum wire electrode were used as a
reference electrode and a counter electrode, respectively. Field
emission scanning electron microscope (FE-SEM) images were
obtained on an S-4800 field emission scanning electron micro-
analyser (Hitachi, Japan). High-performance liquid chromato-
graphy (HPLC, Hitachi L-7100, UV-detector, λ ¼214 nm, VP-ODS
C18 150 mm, t¼ 25 °C, mobile phase 0.5% acetic acid in H2O 10%:
methanol 90%).
2.3. Preparation of pABSA modified GCE (pABSA/GCE)
Prior to the modification, the bare GCE were polished by
0.3 μm alumina slurry on micro-cloth pads and sonicated subse-
quently in water. Then the clean GCE was immersed into 5 mL
phosphate buffer solution (PBS, 0.1 mol/L, pH 7.0) containing
2
10  4 mol/L ABSA. Then CV method was performed from
 1.5 V to þ2.5 V for 15 cycles at a scan rate of 100 mV/s, obtaining
polymer film modified electrode (pABSA/GCE).
2.4. Fabrication of MIP modified pABSA/GCE (MIP/pABSA/GCE)
The prepared pABSA/GCE was immersed into PBS (0.1 mol/L,
pH 5.0) containing 5.0
10  3 mol/L PR and 5.0
10  3 mol/L OPD.
Then CV was performed from 0.0 V to þ0.8 V for 35 cycles at a
scan rate of 75 mV/s, obtaining polymer modified pABSA/GCE.
Subsequently, the embedded PR molecules were extracted by in-
cubating the modified electrode into ethanol for 20 min until no
obvious oxidation peak of PR could be observed by DPV method,
getting MIP modified pABSA/GCE (MIP/pABSA/GCE). The proce-
dure of the fabrication of MIP/pABSA/GCE was depicted in Fig. 1A.
As a control, non-molecular imprinting polymer modified
electrode (NIP/pABSA/GCE) was prepared and treated in exactly
the same way except for the omitting of PR in the electro-
polymerization process. In order to investigate the electrocatalytic
effect of pABSA, other two modified electrodes were prepared by
direct electropolymerization of OPD on GCE surface in the pre-
sence and absence of PR, which were assigned as MIP/GCE and
NIP/GCE, respectively.
2.5. Electrochemical properties measurements
Electrochemical measurements to characterize the prepared
sensor were carried out in PBS by using CV, EIS, and DPV methods.
AA, UA, DA, 4-NP, and HQ were selected as coexisted or structural
similar compounds to evaluate the recognition capacity of the
prepared sensor.
 Y. Teng et al. / Biosensors and Bioelectronics 71 (2015) 137–142 139

Fig. 1. Schematic illustrations of the fabrication procedure of MIP/pABSA/GCE (A) (DPV curves: with the electrocatalysis of pABSA, a higher current response showed on MIP/
pABSA/GCE than that on MIP/GCE), SEM images of pABSA/GCE (B) and MIP/pABSA/GCE (C).

3. Results and discussion

3.1. Electrocatalytic property of pABSA/GCE

Fig. 2 showed the CV curves, which were recorded on bare GCE

and pABSA/GCE in PBS (0.1 mol/L, pH 7.0) with or without
1.0
10  4 mol/L PR. Compared with the CV curve recorded in
blank electrolyte (curve a), an irreversible oxidation peak of PR
could be found on bare GCE at þ0.484 V in accordance with the
reported results (Su and Cheng, 2010) (curve b). Several pairs of
redox peaks appeared in CV curve when it was recorded on
pABSA/GCE in PR solution (curve d). To ascribe these redox peaks,
another CV curve was recorded by immersing pABSA/GCE in blank
electrolyte (curve c). As could be seen, except for a pair of redox
peaks appeared at þ0.458 V and þ0.440 V, other redox peaks
appeared at the same potentials in curve b and curve d, indicating
that these redox peaks were caused by the redox of pABSA itself
and the peaks at þ 0.458 V and þ0.440 V were certainly caused by
the redox of PR, which corresponded to a two-proton and two- Fig. 2. CV curves recorded on bare GCE in the absence of (a) and in the presence of
electron process (Eq. (1)) (Fanjul-Bolado et al., 2009). (b) 1.0
10  4 mol/L PR; CV curves recorded on pABSA/GCE in the absence of
(c) and in the presence of (d) 1.0
10  4 mol/L PR.

the peak current at 0.458 V on pABSA/GCE was about seven times

larger than that on bare GCE. The results of the increase of peak
current and negative shift of oxidized peak potential demonstrated
The oxidation peak of PR shifted negatively about 26 mV and the obvious electrocatalytic characteristics of pABSA for the redox
140 Y. Teng et al. / Biosensors and Bioelectronics 71 (2015) 137–142
of PR, which should improve the sensitivity of the sensor for PR
detection.
3.2. Characterization of MIP/pABSA/GCE
SEM images of pABSA/GCE and MIP/pABSA/GCE shown in
Fig. 1B and C were used to characterize their morphological
structures, respectively. A layer of film with scraggy and uneven
surface was found in Fig. 1B, indicating the pABSA has been elec-
tropolymerized onto the surface of GCE. As MIP film was formed
onto pABSA/GCE, a much rougher surface was observed (Fig. 1C),
which could be attributed to the electropolymerization of MIP
film. The obvious difference on the surface morphologies con-
firmed that two layer of pABSA and MIP films have been succes-
sively prepared onto GCE surface.
Electrochemical impedance spectroscopy (EIS) has been carried
out to investigate the stepwise constructed process of the sensor.
The results were shown in Fig. S1, which also demonstrated the
successfully preparation of the sensor.
In order to investigate the specific adsorption of MIP and the
electrocatalytic effect of pABSA toward the prepared sensor, the
electrochemical responses of PR on MIP/GCE, MIP/pABSA/GCE, and
NIP/pABSA/GCE were recorded using DPV method, as shown in
Fig. 3. Compared with the DPV curve recorded on MIP/GCE (curve
b), peak current increased remarkably when DPV was carried out
on MIP/pABSA/GCE (curve f), demonstrating the high catalytic
activity of pABSA film to the adsorbed PR molecules. It is also
apparent that the MIP/pABSA/GCE displayed a much higher cur-
rent response than that on NIP/pABSA/GCE (curve d) under the
same concentration of PR. The high elecrochemical response of the
imprinted sensor might result from the imprinted cavities in the
MIP and the functional groups in the cavities produced by the
template molecules. Therefore, MIP/pABSA/GCE possessed an
evident specific adsorption capacity and high electrocatalytic ac-
tivity to PR.
The accumulation time was investigated by recording the cur-
rent responses of PR on MIP/pABSA/GCE and MIP/GCE, which were
immersed in PR solution (5.0
10  5 mol/L) for different time. As
shown in Fig. S2, the adsorption of PR on MIP/GCE could not reach
equilibrium within 10 min. Compared with MIP/GCE, MIP/pABSA/
GCE showed a faster accumulation equilibrium time within almost
2 min, which could be attributed to catalysis capacity of the
modified pABSA film in MIP/pABSA/GCE.
Fig. 3. DPV curves recorded on MIP/GCE in the absence of (a) and in the presence
of (b) 1.0
10  4 mol/L PR; DPV curves recorded on NIP/pABSA/GCE in the absence
of (c) and in the presence of (d) 1.0
10  4 mol/L PR; DPV curves recorded on MIP/
pABSA/GCE in the absence of (e) and in the presence of (f) 1.0
10  4 mol/L.
3.3. Optimization of conditions for MIP/pABSA/GCE preparation
Different influencing factors including scan cycles for pABSA
electropolymerization, scan cycles and scan rate for MIP electro-
polymerization, and the molar ratio between template molecule
and monomer were investigated to fabricate an efficient sensor.
DPV was employed to detect the oxidized peak current of PR under
different conditions.
The pABSA film modified on GCE surface was carried out by CV
method with varied scan cycles. As shown in Fig. S3, the peak
current of 1.0
10  4 mol/L PR increased on pABPA/GCE with the
increase of polymerized cycles from 5 to 15, while decreased with
continued increase of the cycles. The reason could be attributed to
two competition effects, i.e., enhancing cation-exchange activity of
coating and suppressing effect due to the thicker polymer that
could reduce the conductivity (Wang et al., 2014a,b).
In the imprinted polymers preparation experiments, an im-
printed factor (IF, the ratio of oxidized peak currents of
1.0
10  4 mol/L PR recorded on MIP/pABSA/GCE and NIP/pABSA/
GCE) was calculated and compared under each condition.
The thickness of the polymer membrane influences the sensi-
tivity of the imprinted electrochemical sensor, which could be
controlled by the scanning cycles. As shown in Fig. S4, the low IF
was obtained when scan cycles was less than 35, which could be
attributed to the formation of fewer imprinted cavities on the
electrode surface. However, the IF decreased while the MIP pre-
pared by scanning over 35 cycles, which probably because PR
molecules could not be removed completely from the polymer
matrix if the imprinted film was too thick. Moreover, accession to
the deeply imprinted sites is difficult for the template molecules
because of the high mass-transfer resistance, which decreases the
detected sensitivity. Therefore, the MIP obtained by scanning 35
cycles achieved the highest sensitivity to PR.
Fig. S5 showed the effect of scan rate for MIP film electro-
polymerization. A tight film would be produced when MIP film
was prepared at a slower scan rate, which decreased the accessi-
bility of template molecule to imprinted sites. The IF on the MIP/
pAPBA/GCE was found to increase with an increase of scan rate up
to 75 mV/s and decrease as the scan rate increased above that
value. A low recognition capacity could be found when a faster
scan rate was performed to get a loose and rough film, which
would decrease the recognition capacity of MIP film. Thus, the
optimum polymerization scan rate was found to be 75 mV/s.
The molar ratio between template molecule and monomer
used in the polymerization process would affect the amount of
imprinted sites in the polymer matrix, further influence the elec-
trochemical behavior of the sensor. A series of MIP/pABSA/GCE
sensors were prepared under different molar ratio between tem-
plate molecules and monomers from 2:1 to 1:3. As shown in Fig.
S6, the IF was found to increase with the increase of molar ratio up
to 1:1. A considerable decrease of IF below and above this molar
ratio was observed. It can be concluded that the optimum molar
ratio between template molecules and monomers was about 1:1.
3.4. Selectivity of MIP/pABSA/GCE
AA, UA, DA, 4-NP, and HQ were selected as interferents to
evaluate the recognition capacity of the prepared sensor. The se-
lective experiments were carried out by detecting the current re-
sponse of 1.0
10  4 mol/L PR or each interferent with the same
concentration of PR on MIPs/pABSA/GCE and NIPs/pABSA/GCE. The
comparison result was illustrated in Fig. 4. Compared with the
current change of AA, UA, DA, and 4-NP on MIPs/pABSA/GCE, the
current resulted from PR with the same concentration showed
much higher current response, and almost no oxidation peak
could be found whether on MIP/pABSA/GCE or NIP/pABSA/GCE
 Y. Teng et al. / Biosensors and Bioelectronics 71 (2015) 137–142
Fig. 4. Selectivity of the sensor. DPV current response recorded on MIP/pABSA/GCE
and NIP/pABSA/GCE in PR or each interferent solution with the same concentration
of 1.0
10  4 mol/L. Each was measured for three repetitive determinations.
(RSD o7.65%). ΔI denoted the difference of currents of DPV curves recorded at
þ 0.45 V with and without PR in the electrolyte.
when the DPV was carried out in the presence of HQ. The reason
may be that the binding sites in imprinted sensor were com-
plementary to PR in terms of the size, shape, and position of their
functional groups. These results demonstrated an acceptable se-
lectivity of the sensor for PR.
3.5. Analytical application of the sensor
The dependence of the oxidation peak current of PR on MIP/
pABSA/GCE was recorded by DPV under the optimized conditions.
As shown in Fig. 5A, the current response increased with the
successive addition of PR. Calibration curve a in Fig. 5B revealed
that the peak currents were proportional to the concentrations of
PR in the range of 5.0
10  8  1.0
10  4 mol/L with a linear re-
gression equation of I (μA) ¼ 0.5310 þ0.171c (μmol/L) (where c is
the concentration of PR). And a detected limit calculated was
4.3
10  8 mol/L. Compare with the linear range and detected
limit reported in previous studies summarized in Table S1, the
present electrochemical sensor showed an excellent detection
capacity to PR. The same detection procedure was carried out on
NIP/pABSA/GCE and MIP/GCE for comparison. The linear range
of 5.0
10  6  1.0
10  4 mol/L obtained on NIP/pABSA/GCE
Fig. 5. DPV curves recorded on MIP/pABSA/GCE with the successive addition of PR (a to l were 5.0
10  8, 1.0
10  7, 5.0
10  7, 1.0
10  6, 3.0
10  6, 5.0
10  6,
7.0
10  6, 1.0
10  5, 3.0
10  5, 5.0
10  5, 7.0
10  5 and 1.0
10  4 mol/L) (A); the calibration plot of the concentration of PR vs. peak current (B) recorded on MIP/
pABSA/GCE (a), NIP/pABSA/GCE (b), and MIP/GCE (c) Each was measured for three repetitive determinations and RSD were calculated to be between 0.48% and 3.57%. ΔI
denoted the difference of currents of DPV curves recorded at þ 0.45 V with and without PR in the electrolyte.
141
(Fig. 5Bb) with a linear regression equation of I (μA)¼ 
0.2327 þ0.058c (μmol/L) was much narrower than that on MIP/
pABSA/GCE, which could be attributed to the imprinted cavities in
MIP/pABSA/GCE for much more PR molecules adsorption. The
same linear range as NIP/pABSA/GCE was obtained on MIP/GCE
(Fig. 5Bc) with a linear regression equation of I (μA)¼
0.7331þ 0.023c (μmol/L). Compared with MIP/GCE and NIP/pAP-
BA/GCE, the highest sensitivity of MIP/pABSA/GCE confirmed the
good electrocatalytic capacity of pABSA and the specific adsorption
capacity of MIP.
To investigate the regeneration of the constructed sensor, MIP/
pABSA/GCE was used to detect 1.0
10  4 mol/L PR for five times
with subsequent cycles of extraction and measuring operations.
According to the current responses, a relative standard deviation
(RSD) was calculated to be 2.58% (Fig. S7a). The reproducibility of
the sensor was investigated by detecting PR on five different MIP/
pABSA/GCE with a RSD of 2.66%, which were prepared under the
same conditions (Fig. S7b).The current response of the imprinted
sensor decreased to 97.6% after storing for 18 days at 4 °C. These
results demonstrated that the prepared sensor had acceptable
reproducibility, regeneration, and stability.
To evaluate the practical performance of the prepared sensor,
two kinds of PR commercial tablets (500 mg/tablet) were de-
termined on MIP/pABSA/GCE. The tablets were ground to powders
and then added with ethanol to dissolve PR. After the cen-
trifugation, the supernate was collected and diluted to a working
concentration range for electrochemical detection. By using the
prepared sensor, the concentration of PR in two kinds of tablets
was determined. As shown in Table 1, the results were in good
agreement with the manufacturers’ stated contents of PR.
Recovery tests were carried out for assay in human urine
samples. The samples were obtained from human after 4 h of
administration of a tablet containing 500 mg of PR. Prior to ana-
lysis, the urine samples were diluted 100 times with PBS. Then the
urine sample was added with a known concentration of PR. Using
the prepared sensor to detect the concentration of PR in different
urine samples before and after spiking, the results obtained were
concluded in Table 1. The results showed that the recoveries from
the urine samples were excellent, and varied from 96.33% to
102.4%. In order to validate the electrochemical detection, we have
detected PR in tablets and human urine samples by HPLC. The
results obtained by HPLC also have been included in Table 1, which
indicated that the prepared sensor can be used as an effective and
reliable sensing platform for detecting PR in real samples.
142 Y. Teng et al. / Biosensors and Bioelectronics 71 (2015) 137–142

Table 1
Determination of PR in tablets and human urine samples.

Samples Labeled (mmol/ Added Detected contentby the sensor Recovery (%) RSD (%) Detected content by HPLC Recovery (%) RSD (%)
L) (mmol/L) (mmol/L) (mmol/L)

Tablet 1 0.30 – 0.31 102.7 1.51 0.29 95.03 1.35

0.50 – 0.52 103.0 3.72 0.49 97.90 5.79

Tablet 2 0.30 – 0.32 105.7 2.74 0.28 91.25 2.51

0.50 – 0.51 102.6 2.31 0.49 99.74 4.07

Urine sample 1 – 0.30 0.31 102.4 5.62 0.31 104.0 4.31

– 0.50 0.49 98.34 4.68 0.51 101.6 1.66

Urine sample 2 – 0.30 0.29 96.33 4.55 0.30 99.36 2.07

– 0.50 0.49 97.40 3.08 0.51 101.9 4.99

4. Conclusion References

In this study, a novel and facile imprinted based electro-
chemical sensor was developed for PR selective recognition and
sensitive detection. A layer of pABSA film electropolymerized onto
GCE surface exhibited high electrocatalytic activity for PR redox,
which remarkably improved the sensitivity of the sensor. The in-
herent property of MIP film endowed the sensor with good se-
lectivity because it could recognize PR from several interferents. A
wide linear range of 5.0
10  8  1.0
10  4 mol/L for PR detection
was obtained with excellent reproducibility and a low detection
limit of 4.3
10  8 mol/L. The proposed sensor could be supposed
to apply in the measurement of PR in commercial tablets and urine
samples. With the advantages of low cost, facile preparation, high
sensitivity, good selectivity, and good stability, the proposed sen-
sor could be developed for other molecules selective recognition
and sensitive detection.
Acknowledgements
We greatly appreciate the support of the National Natural Sci-
ence Foundation of China for young program (21005002), Anhui
Provincial Natural Science Foundation, China for Young Program
(11040606Q35), Anhui University Provincial Natural Science
Foundation Key program (KJ2010A138). We gratefully acknowl-
edge Dr. Yunchun Liu for her kind help in HPLC experiments.
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