Talanta 156-157 (2016) 147153

Contents lists available at ScienceDirect

Talanta
journal homepage: www.elsevier.com/locate/talanta

Polypyrrole nanowire as an excellent solid phase microextraction ber

for bisphenol A analysis in food samples followed by ion mobility
spectrometry
Mahdie Kamalabadi a, Abdorreza Mohammadi b, Naader Alizadeh a,n
a
Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, P.O. Box 14115175, Tehran, Iran
b
Department of Food Science and Technology, National Nutrition and Food Technology Research Institute, Faculty of Nutrition Sciences and Food Technology,
Shahid Beheshti University of Medical Sciences, Tehran, Iran

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

Article history: A polypyrrole nanowire coated ber was prepared and used in head-space solid phase microextraction
Received 29 March 2016 coupled with ion mobility spectrometry (HS-SPME-IMS) to the analysis of bisphenol A (BPA) in canned
Received in revised form food samples, for the rst time. This ber was synthesized by electrochemical oxidation of the monomer
29 April 2016
in aqueous solution. The ber characterization by scanning electron microscopy (SEM) revealed that the
Accepted 2 May 2016
new ber exhibited two-dimensional structures with a nanowire morphology. The effects of important
Available online 3 May 2016
extraction parameters on the efciency of HS-SPME were investigated and optimized. Under the opti-
Keywords: mum conditions, the linearity of 10150 ng g
1 and limit of detection (based on S/N 3) of 1 ng g
1 were
Nanowire obtained in BPA analysis. The repeatability (n5) expressed as the relative standard deviation (RSD%)
Polypyrrole
was 5.8%. At the end, the proposed method was successfully applied to determine BPA in various canned
Bisphenol A
food samples (peas, corns, beans). Relative recoveries were obtained 9396%. Method validation was
Canned food samples
Ion mobility spectrometry conducted by comparing our results with those obtained through HPLC with uorescence detection
Head-space solid phase microextraction (FLD). Compatible results indicate that the proposed method can be successfully used in BPA analysis.
This method is simple and cheaper than chromatographic methods, with no need of extra organic sol-
vent consumption and derivatization prior to sample introduction.
& 2016 Elsevier B.V. All rights reserved.

1. Introduction Environmental Protection Agency established the maximum ac-

Bisphenol A (BPA) is a phenolic compound that mainly used to
manufacture polycarbonate plastic and epoxy resins [1]. Epoxy
resins are used to make protective coatings on metal lids for glass
jars and bottles and linings for food cans [2]. Polycarbonate plas-
tics are often used in some food and drinking packaging such as
water and baby bottles and microwave ovenware. BPA is also an
endocrine disruptor [3,4] and has adverse effect on thyroid func-
tion and other organs and physiological systems [4,5]. BPA is also
classied as a carcinogen and mutagenic compound [6,7]. BPA can
migrate into food or food simulants from the resin or polymeric
materials especially at high temperature. So, the possibility of BPA
migration into canned food is high and due to high consumption
of canned food in the world and adverse effects of BPA on the
human health, determination of BPA is of concern. The specic
migration limit (SML) for BPA in food or food simulant was es-
tablished at 0.6 mg g
1 by the EU Commission [8]. The U.S.
n
Corresponding author.
E-mail address: alizaden@modares.ac.ir (N. Alizadeh).
ceptable dose for BPA at 50 mg kg
1 of body weight/day [8].
The choice of an appropriate sample preparation method for
determination of trace contamination in complex matrix such as
food is very challenging. Sample preparation is a key step in the
analysis and it must reduce the numbers of step, analysis time,
error and matrix effects. Headspace-solid phase microextraction
(HS-SPME) is one of the very useful sample preparation techniques
for the isolation of the target analyte from food matrix [9]. HS-
SPME is a fast, simple and solvent-free technique which integrates
extraction and preconcentration of analytes in a single step. Since
in this approach, the sampling is carried out from the headspace
above the sample, the matrix interferences is reduced, a neat
spectra is obtained and the ber is protected from irreversible
damage by nonvolatile contaminations present in the complex
matrix [10]. However, an extraction or clean up step, followed by a
reconstruction in an aqueous medium is need prior to the mi-
croextraction method in the solid samples [11].
To achieve the selective determination of target analytes in
HS-SPME, the choice of an appropriate ber coating is very im-
portant. In recent years, nanostructured conducting polymers, a
special subclass of conducting polymers, have been attracted much

http://dx.doi.org/10.1016/j.talanta.2016.05.007
0039-9140/& 2016 Elsevier B.V. All rights reserved.
148 M. Kamalabadi et al. / Talanta 156-157 (2016) 147153
attention as novel materials for separation. Nanostructured con-
ducting polymers which have both properties of conducting
polymers and characteristics of nanomaterial have unique prop-
erties including large surface area, accelerated interactions be-
tween the adsorbent and the analyte, increase the capacity and
extraction rates of the adsorbent ber based on conducting poly-
mers [1214]. Polypyrrole (PPy) is one of the most important and
widely used conducting polymers due to its specic properties
such as good environmental stability, high conductivity and facile
synthesis. However, this polymer contains conjugated structure
and can efciently adsorb polar aromatic compounds through -
and hydrophobic interactions. Polypyrrole nanowire (PPy NW) has
attracted much attention because of its higher surface-to-volume
ratio and high aspect ratio (length-to-width ratio) which results in
large stationary phase loading and high extraction capacity [15].
Up to now, the commercial bers such as polydimethylsiloxan/
Divinylebenzene (PDMS/DVB) [16], polydimethylsiloxan (PDMS)
[17] and polyacrylate (PA) [18,19] are used for extraction of BPA. In
this work, we studied PPy NW as a novel HS-SPME ber coating for
extraction of BPA because of the mentioned advantages in above.
To date, several analytical methods including gas chromato-
graphy (GC) [20], high-performance liquid chromatography (HPLC)
[21] capillary electrophoresis (CE) [22], electrochemical sensor
[23] and biosensor [24] have been developed for determination of
BPA from complex samples. These method have advantages and
disadvantages. Ion mobility spectrometry (IMS) have been devel-
oped as a powerful analytical technique for quantitative and
qualitative analysis of analytes in various matrix such as explosives
[25,26], drugs [27], metals [28], biological compounds [29], foods
[30,31] and volatile environmental pollutants [32]. In IMS, the
ionized molecules in the gas phase are separated based on their
mobility in an electric eld at atmospheric pressure. This techni-
que has advantages including low detection limit, fast response,
simplicity and portability and relative low cost. IMS can be oper-
ated in both positive and negative mode. The positive mode show
high sensitivity for analytes with high proton afnity. In corona
discharge ion source, ion formation arises from different paths.
In general, ion formation mechanism in a positive mode with N2
carrier gas are as follows:
N2 +e N2+ +e (primery) + e (secondary) (1)
N2+ + 2N2 N+4 + N2
N+4 + H2 O 2N2 + H2 O+
H2 O+ + H2 O H3 O+ + OH
H3 O+ + H2 O ( H2 O)2 H+
(H2 O)2 H+ + xH2 O (H2 O)x + 2 H+
where (H2 O)x + 2 H+ is dened as cluster reactant ion (RI).
When the analyte (A) has higher proton afnity (PA) than re-
actant ion, protonated molecules (AH ) are formed via proton
transfer reaction, Eq. (7):
(H2 O)x + 2 H+ +AAH+ + (x + 2) H2 O
Phenol has the proton afnity about 817.1 kJ moL
1 that is
higher than hydronium with PA 697.5 kJ moL
1 [33]. So, BPA has
higher proton afnity than RI and protonated BPA (BPAH )
molecules are formed in ion source, Eq. (8):
BPA + H3 O+ BPAH+ +H2 O (8)
The objective of this work was preparation of a novel ber
coating as a SPME adsorbent and development and optimization of
a HS-SPME-IMS for the extraction and determination of BPA in
canned food samples without derivatization step, for the rst time.
To determination of BPA, the effects of the main extraction para-
meters were investigated and optimized. The obtained suitable
results indicate the ability of the proposed method to analysis of
BPA in various canned samples, without sample matrix
interferences.
2. Experimental
2.1. Reagent and chemical
Pyrrole was obtained from Fluka (Buchs, Switzerland) and
distillated before use. Bisphenol A, Sodium dodecyl sulfate (SDS),
methanol, acetone, acetonitrile, hydrochloride acid, sodium hy-
droxide and sodium chloride (analytical grade) were obtained
from Merck (Darmstadt, Germany). Sodium bicarbonate, sodium
perchlorate and ortho-aminophenol (OAP) were purchased from
Sigma-Aldrich (Steinheim, Germany). Stock standard solution
of BPA was prepared at a concentration of 2000 mg mL
1 in
methanol. Standard solution was prepared at concentration of
100 mg mL
1 in double distilled water. Working solutions
(10300 ng mL
1) were prepared by diluting stock solution with
double distilled water. Stock and working solutions were re-
frigerated at 4 C. All solvents were analytical reagent grade or
HPLC grade. The pH of the solutions was adjusted by hydro-
chloride acid.
2.2. Instrumentation
Detection and quantication of BPA was carried out using an
ion mobility spectrometer was manufactured in TOF. Pars Co.
(Iran). The spectrometer was operated in a positive mode. The
optimized experimental conditions for obtaining the ion mobility
spectra of the BPA are listed in Table 1.
The chromatographic analysis was carried out with an Agilent
(2) HPLC instrument (Wilmington, California, USA) equipped with an
Agilent G1315D uorescence detector (FLD) with a 1200 series
quaternary pump. An Agilent Eclipse-XDB-C18 analytical column
(3) (150 mm  4.6 mm, 5 mm) was used for separation of the BPA. The
injection volume was 20 mL, and the column temperature was
25 C (ambient temperature). Separation of BPA was achieved
(4) using acetonitrile/water (50:50, v/v) as mobile phase at a ow
rate of 1.0 mL min
1. FLD monitoring excitation and emission
wavelength was set 225 and 310 nm, respectively.
(5)
Table 1
The optimized experimental ion mobility
spectrometry (IMS) conditions for BPA.
(6)
Parameter Value
Corona current 10 mA
Drift voltage 7000 V
Drift gas ow, N2 380 mL min
1
Carrier gas ow, N2 120 mL min
1
(7) Shutter grid 150 ms
Cell temperature 150 C
Injector temperature 230 C
Drift tube length 11 cm
Drift time 7.8 ms
 M. Kamalabadi et al. / Talanta 156-157 (2016) 147153
The morphology of PPy NW was investigated by a eld-emis-
sion scanning electron microscope (FE-SEM, Carl Zeiss, SIGMA VP,
Germany).
The SPME holder for manual sampling was obtained from Azar
Electrode (Ourumieh, Iran). Electrochemical polymerization of
polymers was carried out by means of AUTOLAB (PGSTAT 30
model) potentiostat. An electrochemical cell including a platinum
(Pt) working electrode (2 cm  300 mm O.D.), a Pt counter elec-
trode and a Ag/AgCl electrode, as reference electrode was used for
preparation of the polymer.
2.3. Preparation of coated SPME bers
The three bers including PPy NW, polypyrrole doped with DS-
(PPy-DS) and poly ortho-aminophenol doped with DS-(POAP-DS)
lms were synthesized by electrochemical polymerization. The
electrochemical polymerizations were carried out using a three
electrode system with a platinum (Pt) working electrode
(2 cm  300 mm O.D.), a Pt counter electrode and, Ag/AgCl elec-
trode as reference electrode. Prior to each electrochemical poly-
merization, the synthesis solution was deoxygenated by purging it
with nitrogen for 10 min and the working electrode was cleaned in
methanol, acetone and water using an ultrasonic bath for 10 min,
respectively. Finally, it was dried in room temperature before
performing the experiments.
The PPy NW is obtained in the presence of weak-acid anions
[34]. PPy NW was directly electrodeposited on the surface of a Pt
wire from an aqueous solution containing pyrrole (0.1 mol L
1)
and NaClO4 (0.1 mol L
1), Na2CO3 (0.1 mol L
1) and SDS
(5  10
4 mol L
1) takes place at 0.8 V vs. Ag/AgCl for 600 s The
preparation procedure for PPy-DS was similar to those of PPy NW
with the exception that solution was containing only pyrrole
(0.1 mol L
1) and SDS (7  10
3 mol L
1). The POAP-DS lm was
synthesized using a solution containing OAP (0.05 mol L
1) and
SDS (7  10
3 mol L
1) in the presence of 1 mol L
1 HCl. POAP-DS
was potentiodynamically obtained after 50 cycles in the potential
range:
0.20 to 1.20 V vs. Ag/AgCl at the rate of 100 mV/s. After
polymerization, the bers were heated at 100 C for 30 min in an
oven and nally conditioned at 240 C in an IMS injection port
under nitrogen gas for 1 h, before they were used for SMPE
experiment.
2.4. Sample preparation and HS-SPME-IMS analysis of real samples
All of the canned food samples (peas, bean, and corn) were
purchased from different local supermarkets in Tehran. The solid
sample was minced in a blender. Then, 2.5 g of homogenized
sample was mixed and shacked with 2.5 mL of acetonitrile/water
(10:90, v/v) for 2 min After centrifuging for 4 min in 4500 rpm, the
liquid phase was collected and the solid residue was re-extracted
with 2.5 mL of acetonitrile/water (10:90, v/v). Both liquid phases
were combined in a volumetric ask and the nal volume was
adjusted to 5 mL with acetonitrile/water (10:90, v/v).
In the next step, 5 mL of sample solution was mixed with
200 mL of HCl (2 mol L
1, in order to pH 2) in a glass vial and
after adding sodium chloride and a magnetic stir bar; the vial was
accurately closed with a PTFE/silicon septum and tightly sealed
with an aluminum seal. The vial was heated in a water bath at
60 C and the PPy NW ber was exposed to the headspace over the
stirring liquid sample for 20 min After sampling step, the ber was
withdrawn into the needle and then immediately inserted into the
injection port of the IMS (adjusted at 230 C) for thermal deso-
rption and analysis of the analytes. In order to conrm the absence
of contaminants and memory effect, the ber was inserted in the
IMS injection. It was found BPA fully desorbed from the ber
coating after 2 min and no carry over effect was observed in blank
149
injections. All analyzed were repeated three times for each sample.
2.5. Sample preparation of real samples for HPLC analysis
1 g of minced sample was mixed with 1 mL of acetonitrile and
shacked for 2 min This mixture was centrifuged at 4500 rpm for
4 min Then, the liquid phase was separated and the solid residue
was extracted with 1 mL of acetonitrile for two times. Both liquid
phases were combined and ltered. Finally, 20 mL of the liquid
phase obtained was injected into the HPLC.
3. Result and discussion
3.1. Selection solvent of solvent extraction in sample preparation
Determination of BPA in food samples requires a previous ex-
traction or cleaning step such as solvent extraction before micro-
extraction techniques due to complication of matrix [35]. Since the
type of solvent can be affected on the extraction efciency, we
investigated the effect of solvents such as water, acetonitrile/water
5%, 10% and 15% with pH 11 (in order to hydrolyze and saponify
sample and extraction of BPA from sample matrix). As seen in
Fig. 1, the highest extraction efciency was obtained using acet-
onitrile/water 10%. So, this solution was used as the best solvent in
sample retreatment.
3.2. HS-SPME optimization
HSSPME is an equilibrium process including the partitioning
of analytes from aqueous phase to the headspace and into the ber
coating according to their partition coefcients. Thus, the optimi-
zation of parameters that inuence the partition of analytes be-
tween the headspace and the solution are very important. The
effects of important parameters that affect extraction efciency
such as ber type, sample pH, ionic strength, extraction time and
extraction temperature were investigated and optimized. All ex-
tractions were performed from the headspace of standard solu-
tions of BPA at concentration of 50 ng mL
1. In order to improve
mass transfer in the aqueous phase and to induce the convection
in the headspace, all experiments were performed at 700 rpm
stirring speed.
3.2.1. Fiber selection
Fiber coatings control the extraction efciency of analytes. The
polar coatings such as polydimethylsiloxan/Divinylebenzene
(PDMS/DVB), polydimethylsiloxan (PDMS) and polyacrylate (PA)
are most popular ber coatings for extraction of BPA. In this study,
three ber coatings were constructed and tested for preliminary
investigation: PPy-DS, POAP-DS and PPy NW. The extraction ability
of the three mentioned bers was evaluated by comparison the
Fig. 1. The effect of solvent type in sample treatment.
150 M. Kamalabadi et al. / Talanta 156-157 (2016) 147153
Fig. 2. Calibration curves for PPy NW, POAP-DS and PPy-DS bers.
sensitivity of extraction of BPA. The selected polymers contain a
conjugated structure and therefore, there is an exception that
they efciently extract polar aromatic compounds easily through
- and hydrophobic interactions. As shown in Fig. 2, the PPy NW
has the higher extraction ability and calibration sensitivity for the
BPA than other bers due to higher volume-to-surface ratio. Also,
POAP-DS shows a higher sensitivity than PPy-DS. This result can
refer to present polar substituents on the surface of polymer that
cause additional interactions such as hydrogen bonding between
polymer and analyte. So, the PPy NW was used as the SPME ber
coating for the extraction of BPA due to the most sensitivity.
The PPy NW lm was characterized using FE-SEM. Fig. 3 shows
the PPy two-dimensional structure with a nanowire morphology
on the surface of Pt wire. However, the FE-SEM images show that
the PPy NW lm is highly porous due to the uniform shape of the
PPy NW and has very high surface area [34,36]. Then, the PPy NW
is a ber with large stationary phase loading and high extraction
capacity due to very high surface area. Thermal stability is an
important characteristic in application of SPME bers. The thermal
Fig. 3. Scanning microscopy images of the polypyrrole nanowire ber at 200 (a), 1000 (b), 20,000 (c) and 50,000 (d) folds magnication.
stability of the PPy NW ber was investigated by introducing the
ber into the IMS injector at temperatures of 200, 220 and 250 C.
The PPy NW ber was found to be stable up to 250 C without any
signicant thermal decomposition. Also, it was found that the
extraction peak area remain more or less the same after the ber
was conditioned at temperatures 220 and 250 C, successively.
The lifetime is one of important SPME ber characteristics.
Therefore, the lifetime of PPy NW ber was evaluated by per-
forming the calibration sensitivity repeatability tests under opti-
mum conditions. The ber was used more than 17 times at 230 C
with a relative standard deviation (RSD) r6%. It was still stable
and reusable.
3.2.2. pH sample
The sample pH is the most important parameter affecting
analyze of the polar compounds from aqueous solutions using HS-
SPME method. In this way, the effect of the pH of sample solution
on the extraction efciency of BPA was investigated in range of 28
(Fig. 4a). Since the dissociation of BPA is suppressed at acidic
conditions, the maximum extraction efciency was obtained at
pH 2. Thus, the all experiments were performed at pH 2.
3.2.3. Extraction temperature
The extraction temperature was investigated in range 3070 C.
Fig. 4(b) shows an increase at the extraction efciency for the
diffusion of analyte from solution into the head-space above the
sample enhances when the temperature increases. However, a
decrease in the extraction efciency was observed at the tem-
perature over 60 C. This is because the adsorption is an exother-
mic process and therefore, the partition coefcient of analytes
between the headspace and ber decreases. Thus, the extraction
temperature of 60 C was selected as the best temperature for
further analyses.
 M. Kamalabadi et al. / Talanta 156-157 (2016) 147153 151

Fig. 4. a. The effect of sample pH on the extraction efciency (n 3). Experimental conditions: extraction temperature: 50 C; extraction time: 30 min; salt concentration:
12% (w/v); stirring speed: 700 rpm. b. The effect of extraction temperature on the extraction efciency (n 3). Experimental conditions: pH: 2; extraction time: 30 min; salt
concentration: 12% (w/v); stirring speed: 700 rpm. c. The effect of salt effect on the extraction efciency (n 3). Experimental conditions: pH: 2; extraction temperature:
60 C; extraction time: 30 min; stirring speed: 700 rpm. d. The effect of extraction time on the extraction efciency (n 3). Experimental conditions: pH: 2; extraction
temperature: 60 C; salt concentration: 18% (w/v); stirring speed: 700 rpm.

3.2.4. Salt effect 3.4. Quantitative analysis

The inuence of salt addition on the extraction efciency was
also investigated. As can be seen in Fig. 4(c), the extraction ef-
ciency of BPA increases with increasing NaCl concentration from
0 to 18% (w/v) and then, remains constant. The present of a salt in
an aqueous solution increases the ionic strength (salting out ef-
fect). As a consequence, the solubility of the polar compounds such
as BPA is decreased and the distribution constant of analyte be-
tween the aqueous phase and the headspace is enhanced. So, 18%
of NaCl concentration was chosen as the optimum salt amount.
3.2.5. Extraction time
The extraction time is a major parameter affecting the extrac-
tion efciency in the HS-SPME method. Because HS-SPME is an
equilibrium process of analytes between the headspace and the
ber. As a consequence, there is a direct relationship between the
extraction time and the extracted analyte amount. So, the effect of
the extraction time was examined in range 1030 min
Fig. 4(d), shows extraction equilibrium curve and the best ex-
traction efciency is achieved at 20 min
3.3. Study of repeatability and reproducibility
The repeatability (for one ber) was obtained through per-
forming ve replicate analysis under same conditions from a
canned food sample. The RSD% was 5.8%. To evaluate the ber-to-
ber reproducibility, three different bers were prepared under
the same synthetic conditions and ve replicate analysis were
performed by each ber. RSD% was 8.3%. This result is an evidence
that the proposed method for construction of the ber possesses a
good reproducibility.
Some useful analytical parameters were determined for the
method used. These parameters, including dynamic linear range
(DLR), coefcient regression (R2), limit of detection (LOD), limit of
quantitation (LOQ) and relative recovery (RR) were obtained under
the optimum conditions from a canned sample.
The proposed HS-SPME-IMS procedure showed a good linear
behavior in the concentration range of 10150 ng g
1, with coef-
cient of determination better than 0.994. The limit of detection
(based on S/N 3) and limit of quantitation (based on S/N 10) by
using the PPy NW ber in BPA analysis were 1 ng g
1 and
3 ng g
1, respectively.
In order to estimate the accuracy of the proposed method, the
percentage recovery for BPA was determined by adding known
concentration (30 and 80 ng g
1) of the target analyte to a real
sample and extracting it at the optimum conditions. The obtained
relative recovery values were determined by comparing the ex-
pected and calculated concentrations. The recovery values were
between 93% and 96%. A comparison between obtained gures of
merit by the proposed method and previous literatures for ex-
traction and determination of BPA in food samples is given in
Table 2. It clearly shows that the present method has advantages
including a good sensitivity, speed, precision and simplicity.
Also, the obtained LODs by our proposed method are comparable
or better than those in the previous reported methods [1,18,
37-40], Table 2.
3.5. Analysis of BPA in canned samples by HS-SPME-IMS
In order to evaluate the applicability of this method, HS-SPME-
IMS was used to determine of BPA in various canned food samples
152 M. Kamalabadi et al. / Talanta 156-157 (2016) 147153

Table 2
Comparison dynamic linear range (DLR), repeatability (RSD%), recovery, limit of detection (LOD) and limit of quantication (LOQ) for the analysis of BPA in canned food
samples using proposed and other methods.

Method Matrix DLR (ng g
1) LOD (ng g
1) LOQ (ng g
1) RSD Recovery (%) Ref.

SPME-HPLC Aqueous foods 10500 1.1 3.8 22 [37]

SPME-GC-MS Canned foods 0.110 0.025 0.083 5.4 [1]
MISPE-CEa Beverages 3.0300 0.80 3 88103 [38]
SBSE-GCMSb Canned beverages 0.0025 0.0084 1.9 [39]
GC-MS Canned food 5700 2 7 81103 [40]
HS-SPME- GC-MS Water samples 1100 1.8 104.9 [18]
HS-SPME-IMS Canned foods 10150 1 3 5.8 9396 This work

a
On-line molecularly imprinted solid-phase extraction coupled with capillary electrophoresis.
b
Stir bar sorptive extraction coupled to gas chromatographymass spectrometry.

Table 3 SPME-IMS for the analysis of BPA in the food samples.

Analytical results of BPA in canned food by HS-SPME-IMS method and comparing
with the obtained results using HPLC-FLD method.

Canned food Expiration datea BPA (ng g
1) BPA (ng g
1) 4. Conclusion

HS-SPME-IMS HPLC-FLD A PPy NW SPME ber was electrochemically synthesized. This

ber showed a high capacity loading and sensitivity for determi-
Bean1 July 2017 340 7 20 4007 7
Bean2 May 2014 6977 40 628 7 12 nation of BPA by HS-SPME followed by IMS. This is because of high
Corn1 September 2017 184 7 11 2117 4 surface to volume and high aspect ratio in PPy NW. Good thermal
Corn 2 November 2016 3917 22 4437 7 stability and adhesion to Pt are another advantages of PPy NW. The
Peas1 March 2017 1527 9 1377 3
low detection, good precision and high recoveries are obtained by
Peas 2 March 2016 2157 13 1887 3
the proposed method. These results show that PPy NW is a sui-
a
Expiration date is 2 years after production date. table alternative to the commercial and some of synthesis bers
for the detection of BPA in complicated samples. As a consequence,
the HS-SPME-IMS is an effective, precise, simple, fast, solvent-free
and low cost method for extraction and detection of BPA in com-
plicated samples such as canned food without any derivatization
steps.

Acknowledgement

This work has been supported by grants from the Tarbiat

Modares University Research Council, which is hereby gratefully
acknowledged.

Fig. 5. The ion mobility spectrum obtained by HS-SPME using a PPy NW lm from
headspace of a real sample (peas1) under optimum conditions. References

purchased from different supermarkets in Tehran. The solid por-
tion of canned foods was analyzed under the optimum conditions.
The obtained results are given in the Table 3. BPA was detected in
the all samples. BPA concentration was less than European Union
migration limit of 0.6 mg of BPA/g of food in all but one sample
(Bean2). The storage time as a factor inuencing migration of BPA
from cans was also investigated. The results showed the migration
level of BPA increases with increasing storage time.
Fig. 5 shows a typical spectrum obtained by HS-SPME-IMS
under the optimum conditions for a real sample (peas1). A clean
separation and a good spectrum is easily achieved without the
presence of sample matrix interference.
3.6. Method validation
In order to valid the proposed method, the BPA level in the
same real samples that were applied in 35 section, were de-
termined with HPLC-FLD. The results obtained by HS-SPME-IMS
was compared with those obtained from HPLC-FLD experiments.
As it was shown in Table 3, there is a good correlation between
these results and this accordance conrms the suitability of HS-
[1] P. Vias, N. Campillo, N. Martnez-Castillo, M. Hernndez-Crdoba, Compar-
ison of two derivatization-based methods for solid-phase microextractiongas
chromatographymass spectrometric determination of bisphenol A, bisphenol
S and biphenol migrated from food cans, Anal. Bioanal. Chem. 397 (2010)
115125.
[2] L.N. Vandenberg, R. Hauser, M. Marcus, N. Olea, W.V. Welshons, Human ex-
posure to bisphenol A (BPA), Reprod. Toxicol. 24 (2007) 139177.
[3] P. Sohoni, J. Sumpter, Several environmental oestrogens are also anti-andro-
gens, J. Endocrinol. 158 (1998) 327339.
[4] Y.B. Wetherill, B.T. Akingbemi, J. Kanno, J.A. McLachlan, A. Nadal,
C. Sonnenschein, C.S. Watson, R.T. Zoeller, S.M. Belcher, In vitro molecular
mechanisms of bisphenol A action, Reprod. Toxicol. 24 (2007) 178198.
[5] K. Moriyama, T. Tagami, T. Akamizu, T. Usui, M. Saijo, N. Kanamoto, Y. Hataya,
A. Shimatsu, H. Kuzuya, K. Nakao, Thyroid hormone action is disrupted by
bisphenol A as an antagonist, J. Clin. Endocrinol. Metab. 87 (2002) 51855190.
[6] A.M. Calafat, Z. Kuklenyik, J.A. Reidy, S.P. Caudill, J. Ekong, L.L. Needham, Ur-
inary concentrations of bisphenol A and 4-nonylphenol in a human reference
population, Environ. Health Perspect. (2005) 391395.
[7] A.V. Krishnan, P. Stathis, S.F. Permuth, L. Tokes, D. Feldman, Bisphenol-A: an
estrogenic substance is released from polycarbonate asks during autoclaving,
Endocrinology 132 (1993) 22792286.
[8] . Sungur, M. Krolu, A. zkan, Determinaton of bisphenol a migrating from
canned food and beverages in markets, Food Chem. 142 (2014) 8791.
[9] W. Wardencki, M. Michulec, J. Curyo, A review of theoretical and practical
aspects of solid-phase microextraction in food analysis, Int. J. Food Sci. Tech-
nol. 39 (2004) 703717.
[10] S. Ulrich, Solid-phase microextraction in biomedical analysis, J. Chromatogr. A
902 (2000) 167194.
 M. Kamalabadi et al. / Talanta 156-157 (2016) 147153
[11] C. Yang, J. Wang, D. Li, Microextraction techniques for the determination of
volatile and semivolatile organic compounds from plants: a review, Anal.
Chim. Acta 799 (2013) 822.
[12] F. Zhang, T. Nyberg, O. Ingans, Conducting polymer nanowires and nanodots
made with soft lithography, Nano Lett. 2 (2002) 13731377.
[13] J.I. Lee, S.H. Cho, S.-M. Park, J.K. Kim, J.K. Kim, J.-W. Yu, Y.C. Kim, T.P. Russell,
Highly aligned ultrahigh density arrays of conducting polymer nanorods using
block copolymer templates, Nano Lett. 8 (2008) 23152320.
[14] M. Wan, A template-free method towards conducting polymer nanostructures,
Adv. Mater. 20 (2008) 29262932.
[15] Q. Zhao, Q. Lu, Y.-Q. Feng, Dispersive microextraction based on magnetic
polypyrrole nanowires for the fast determination of pesticide residues in
beverage and environmental water samples, Anal. Bioanal. Chem. 405 (2013)
47654776.
[16] C. Martnez, N. Ramrez, V. Gmez, E. Pocurull, F. Borrull, Simultaneous de-
termination of 76 micropollutants in water samples by headspace solid phase
microextraction and gas chromatographymass spectrometry, Talanta 116
(2013) 937945.
[17] I. Limam, A. Guenne, M.R. Driss, L. Mazas, Simultaneous determination of
phenol, methylphenols, chlorophenols and bisphenol-A by headspace solid-
phase microextraction-gas chromatography-mass spectrometry in water
samples and industrial efuents, Int. J. Environ. Anal. Chem. 90 (2010)
230244.
[18] M.I. Helaleh, S. Fujii, T. Korenaga, Column silylation method for determining
endocrine disruptors from environmental water samples by solid phase mi-
cro-extraction, Talanta 54 (2001) 10391047.
[19] X. Li, L. Lin, S. Zou, C. Lan, T. Luan, Determination of bisphenol A in landll
leachate by solid phase microextraction with headspace derivatization and gas
chromatography-mass spectrophotometry, Chin. J. Anal. Chem. 34 (2006)
325328.
[20] J. Lu, J. Wu, P.J. Stoffella, P.C. Wilson, Analysis of bisphenol A, nonylphenol, and
natural estrogens in vegetables and fruits using gas chromatographytandem
mass spectrometry, J. Agr. Food Chem. 61 (2012) 8489.
[21] T. Lv, X.E. Zhao, S. Zhu, F. Qu, C. Song, J. You, Y. Suo, Determination of bisphenol
A, 4octylphenol, and 4nonylphenol in soft drinks and dairy products by
ultrasound-assisted dispersive liquidliquid microextraction combined with
derivatization and high-performance liquid chromatography with uores-
cence detection, J. Sep. Sci. 37 (2014) 27572763.
[22] H. Wang, A. Zhang, W. Wang, M. Zhang, H. Liu, X. Wang, Separation and De-
termination of triclosan and bisphenol a in water, beverage, and urine samples
by dispersive liquidliquid microextraction combined with capillary zone
electrophoresisuv detection, J. AOAC Int. 96 (2013) 459465.
[23] K.-J. Huang, Y.-J. Liu, Y.-M. Liu, L.-L. Wang, Morphology of template-grown
polyaniline nanowires and its effect on the electrochemical capacitance of
nanowire arrays, J. Hazard. Mater. 276 (2014) 207215.
[24] K.-J. Huang, Y.-J. Liu, G.-W. Shi, X.-R. Yang, Y.-M. Liu, Label-free aptamer sensor
for 17-estradiol based on vanadium disulde nanoowers and Au nano-
particles, Sens, Actuators B: Chem. 201 (2014) 579585.
[25] M. Tabrizchi, V. ILbeigi, Detection of explosives by positive corona discharge
ion mobility spectrometry, J. Hazard. Mater. 176 (2010) 692696.
153
[26] H. Lai, A. Leung, M. Magee, J.R. Almirall, Identication of volatile chemical
signatures from plastic explosives by SPME-GC/MS and detection by ion
mobility spectrometry, Anal. Bioanal. Chem. 396 (2010) 29973007.
[27] N. Alizadeh, E. Samaei, H. Kalhor, Electrochemically controlled solid phase
microextraction of ibuprofen based on nanostructure conducting molecular
imprinted polypyrrole and selective analysis in biological and formulation
samples using ion mobility spectrometry, Anal. Methods 6 (2014) 29092915.
[28] P. Shahdousti, N. Alizadeh, Headspace-solid phase microextraction of sele-
nium (IV) from human blood and water samples using polypyrrole lm and
analysis with ion mobility spectrometry, Anal. Chim. Acta 684 (2011) 6771.
[29] H. Kalhor, N. Alizadeh, Determining urea levels in dialysis human serum by
means of headspace solid phase microextraction coupled with ion mobility
spectrometry and on the basis of nanostructured polypyrrole lm, Anal.
Bioanal. Chem. 405 (2013) 53335339.
[30] M. Kamalabadi, E. Ghaemi, A. Mohammadi, N. Alizadeh, Determination of
furfural and hydroxymethylfurfural from baby formula using headspace solid
phase microextraction based on nanostructured polypyrrole ber coupled
with ion mobility spectrometry, Food Chem. 181 (2015) 7277.
[31] Z. Karpas, B. Tilman, R. Gdalevsky, A. Lorber, Determination of volatile bio-
genic amines in muscle food products by ion mobility spectrometry, Anal.
Chim. Acta 463 (2002) 155163.
[32] N. Alizadeh, M. Jafari, A. Mohammadi, Headspace-solid-phase microextraction
using a dodecylsulfate-doped polypyrrole lm coupled to ion mobility spec-
trometry for analysis methyl tert-butyl ether in water and gasoline, J. Hazard.
Mater. 169 (2009) 861867.
[33] S.M. Collyer, T.B. McMahon, Proton afnity of water. A scale of gas-phase ba-
sicities including ethylene and water from ion cyclotron resonance proton
transfer equilibrium measurements, J. Phys. Chem. 87 (1983) 909911.
[34] Y. Tian, J. Wang, Z. Wang, S. Wang, Solid-phase extraction and amperometric
determination of nitrite with polypyrrole nanowire modied electrodes Sens,
Actuators B: Chem. 104 (2005) 2328.
[35] A. Ballesteros-Gmez, S. Rubio, D. Prez-Bendito, Analytical methods for the
determination of bisphenol A in food, J. Chromatogr. A 1216 (2009) 449469.
[36] L. Al-Mashat, C. Debiemme-Chouvy, S. Borensztajn, W. Wlodarski, Electro-
polymerized polypyrrole nanowires for hydrogen gas sensing, J. Phys. Chem. C
116 (2012) 1338813394.
[37] C. Nern, M. Philo, J. Salafranca, L. Castle, Determination of bisphenol-type
contaminants from food packaging materials in aqueous foods by solid-phase
microextractionhigh-performance liquid chromatography, J. Chromatogr. A
963 (2002) 375380.
[38] X. Zhang, D. Zhu, C. Huang, Y. Sun, Y.-I. Lee, Sensitive detection of bisphenol A
in complex samples by in-column molecularly imprinted solid-phase extrac-
tion coupled with capillary electrophoresis, Microchem. J. 121 (2015) 15.
[39] J. Cacho, N. Campillo, P. Vias, M. Hernndez-Crdoba, Stir bar sorptive ex-
traction coupled to gas chromatographymass spectrometry for the determi-
nation of bisphenols in canned beverages and lling liquids of canned vege-
tables, J. Chromatogr. A 1247 (2012) 146153.
[40] A. Goodson, W. Summereld, I. Cooper, Survey of bisphenol A and bisphenol F
in canned foods, Food Addit. Contam. 19 (2002) 796802.