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An enantioselective polyaniline-coated membrane electrode based on chiral

salen Mn(III) as chiral selector

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Published on 23 February 2012 on http://pubs.rsc.org | doi:10.1039/C2AY05820K

Lan Xu,* Jingya Hou, Yuanyuan Yang, Bingxin Li and Shaozhu Chen
Received 24th November 2011, Accepted 20th January 2012
DOI: 10.1039/c2ay05820k
A novel ion-selective electrode for chiral determination of mandelic acid (MA) is constructed of
a poly(vinyl chloride) (PVC) membrane doped with a chiral salen Mn(III) compound as chiral selector
and coated with a chemically generated film of polyaniline (PANI). The developed sensor displays
a linear response towards L-MA over a wide concentration range of 1.0
101 to 1.0
106 M with
Nernstian slope of 57.6 mV per decade and the detection limit of 2.1
107 M. Ascribed to the
hydration of PANI, it demonstrates a better potentiometric characteristic (especially, linear range,
detective limit, response time) in contrast to the uncoated membrane based sensor.

1. Introduction
The chirality of enantiomers has attracted great interest worldwide as the majority of bioorganic molecules in living organisms
are chiral.1 Moreover, chiral compounds have significant differences in kinetics, metabolism and stability behavior.2 Accordingly, the development of analytical methods to evaluate the
enantiomeric purity is a critical important task. Nowadays, many
separation techniques and test methods are based on chromatography, capillary zone electrophoresis,3,4 mass spectrometry
and more recently, electrochemistry.5 However, the use of
chromatographic and spectrophotometric techniques is laborious, time-consuming, requiring several chemicals and needing
chemical pre-treatments of samples. Advantageously, electrochemical techniques feature relatively high efficiency, simplicity
and low cost. Recently, voltammetry electrochemical methods
were introduced for the determination of optical active
compounds using chiral solvents and supporting electrolytes,6,7
electrodes with a chiral surface8 and inorganic materials.9
Enantioselective potentiometric sensors have been addressed
based on chiral selectors, such as cyclodextrins,10 maltodextrins,11,12 crown ethers and macrocyclic antibiotics, in which the
enantio-recognition mechanism was mainly due to three points
binding and lock and key rules.
Enantiomers of mandelic acid (MA) are valuable chemicals
that have been utilized extensively for synthetic purposes13 as
well as the resolution of racemic alcohols and amines.14,15 Some
studies showed that chiral salen Mn(III) compound is an efficient
chiral selector for enantioselective potentiometric sensing of

Key Laboratory on Luminescence and Real-Time Analysis, Ministry of

Education, School of Chemistry and Chemical Engineering, Southwest
University, Chongqing, 400715, PR China. E-mail: xulan@swu.edu.cn;
Fax: +86-23-68254000; Tel: +86-23-68253544

This journal is The Royal Society of Chemistry 2012

L-MA with a enantio-recognition mechanism based on stereorecognition power of the active chiral salen Mn(III).16
In recent years, polyaniline (PANI), as a conducting polymer,
has received increasing attention as one of the most intensively
studied chemical materials in electrochemical sensor applications. In the development of potentiometric sensors, PANI has
been successfully used as a solid contact between transducer and
an ion-selective membrane,17,18 and a component of an ionselective membrane matrix.19,20 PANI films deposited on noblemetal or polymeric supports are easily produced in situ during the
polymerization of PANI.21 Shishkanova and his co-workers have
reported an enhancement of the potentiometric response of the
PVC membrane after coating with PANI.22 As an outer layer on
a plasticized PVC membrane surface, PANI could favor the
transport of highly hydrated sulfates from aqueous medium.
In the present study, a PANI film was deposited on PVC
membrane surface in order to improve potentiometric behavior
of an ion-selective electrode (ISE) based on chiral salen Mn(III)
complex for determination of chiral mandelic acid anion. The
coated PVC-Mn(salen) membrane sensor displayed an observable improved performance, especially, linear range, detective
limit, response time, compared with the uncoated membrane
owing to the highly hydrated mandelic acid anions from aqueous
medium.

2. Experimental
2.1 Reagents
High molecular weight poly(vinyl chloride) (PVC), tetrahydrofuran (THF), D-mandelic acid (D-MA) and L-mandelic acid
(L-MA) were obtained from Tianjin Kermel chemical reagent
Limited company. Aniline, o-nitrophenyloctylether (o-NPOE)
and ammonium peroxydisulfate were purchased from Alfa
Aesar. Acids, sodium hydroxide and inorganic salts were
Anal. Methods, 2012, 4, 807811 | 807

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supplied by Chengdu kalong chemical reagent company.

Chiral salen Mn(III) was synthesized and purified according to
previous literature.23 All chemical reagents were analytical grade
and doubly distilled water was used for preparing all aqueous
solutions. Different concentrations of MA solutions were
obtained by diluting stock solution (0.1 M). All stock solutions
and diluted solutions were buffered with phosphate buffer
solution.

SCE | test solution | PVC membrane | the inner solution | Ag/

AgCl.
The potentials were measured by varying the concentration of
the test solution in the range 0.5
106 to 1.0
101 M.
Potentiometric enantioselective coefficient was determined by the
modified separate solution method ([MSSM])26 and fixed
interference method ([FIM]).27 For MSSM, the potentiometric
enantioselective coefficient is evaluated by the following
equation:28

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Published on 23 February 2012 on http://pubs.rsc.org | doi:10.1039/C2AY05820K

2.2 Apparatus
All potentiometric and pH measurements were made with a pH
meter (Model pHS-3C, Leici Instruments, Shanghai, China).
A saturated calomel electrode (SCE) was used as a reference
electrode. The pH was monitored using a glass electrode
(Type E-900, Hongyi Instruments and Meters, Shanghai, China).
X-ray instrument (XRD-3, Puxi Instruments, Beijing, China)
was used to carry out the X-ray diffraction experiments of the
PANI layers at ambient temperature.

Pot
log KL;D

ED  EL
S

(1)

Where ED, EL mean the potential response at the 0.1 M D-MA

and L-MA solution, respectively, and S denotes a slope of
calibration curves.
For FIS method, an entire calibration curve is measured for
varying concentration of the primary ion ([L-MA]) in a constant
concentration of the interfering ion ([D-MA]) background. The
value of Kpot
L-MA, D-MA can be calculated from the following
equation:

2.3 Preparation of PVC membranes

The PVC-based membranes were prepared by dissolving 1.6 wt%
PVC powder, 64.6 wt% plasticizer (o-NPOE) and 3.8 wt%
ionosphere, chiral salen Mn(III) in freshly distilled THF. Then the
resulting mixture solution was transferred into a glass plate with
2 cm diameter. The solvent was evaporated slowly at room
temperature until a transparent, homogenous membrane
approximately 0.15 mm thick was formed. A 15 mm diameter
disc was cut out from the resulting polymeric film for ion-selective membranes.
2.4 Preparation of PANI coated membranes21,24
The PANI coating was prepared by polymerization in the freshly
prepared 1 : 1(v/v) mixture of 0.5 M aniline hydrochloride
(monomer) and 0.4 M ammonium peroxydisulfate (initiator) in
the presence of a piece of PVC membrane. Coating was
completed within several minutes. A green film was grown on
both sides of the plasticized PVC membrane. Then the PANIcoated membrane was rinsed with 100 mL portions of 1.5 M
HCl, treated ultrasonically for 10 min in 1.5 M HCl aqueous
solution and dried at ambient temperature. As Gospodinovas
report,25 during the aniline polymerization, a thin PANI film was
formed with a thickness of about 100200 nm. A strip of
the sample was immersed again in a new reaction mixture and the
coating was repeated for a second time, and similarly for the
third time.

KLpot
-MA;D-MA

L-MA
D-MA

(2)

2.6 Characterization of the PVC-membrane surface

X-ray diffraction experiments of the PANI layers were
carried out at ambient temperature using XD-3 diffractometer
in reflection and transmission modes (Cu-Ka radiation,


l 1.5406 A).
The hydrophilicity of PVC membrane surface was
evaluated by water contact angles, which were determined
with a Contact Angle Measuring System OCA 20 at 20  C
under atmospheric conditions by formation of a 4 mL drop
of water on the surface. For each sample, at least three
measurements on different locations were taken, and the
results were averaged.

2.5 The fabrication of electrodes and emf measurements

The PVC membrane was cut to size and attached to one end of
PVC the tube. Subsequently, the tube was filled with an internal
reference solution. A silver/silver chloride electrode was used as
the internal reference electrode.
Before the potentiometric measurements, the PANI-coated
membranes were immersed in 2
102 M NaOH for 10 min,
then washed with distilled water.
All emf measurements were carried out with the following cell
assembly:
808 | Anal. Methods, 2012, 4, 807811

Fig. 1 X-ray of PANI coated on PVC membrane.

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3. Results and discussion

3.1 The character of PANI membrane
According to X-ray analysis (Fig. 1), an amorphous structure of
the PANI particles coating the PVC membrane was monitored.
Thus PANI layer was not a densely packed film. It is reasonable
to assume that the transport of low molecular species in such
structure may take place through inter-particle spaces.

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3.2 The hydrophilicity of PANI-coated membrane

The hydrophilicity of the surface of PVC membrane before and
after coating with PANI film was assessed by determining water
contact angles. As Fig. 2 shows, the experimental values of the
contact angles obtained for an uncoated PVC membrane was
82 . After coating with PANI, the value was decreased to 55 . It
is thus clear that the hydrophilicity of the membrane surface
obviously increases.
3.3 Optimization of PANI film
For PANI coated membrane electrode, the potential response
obtained for a given membrane not only significantly depends on
the nature of the chiral selector, the amount of chiral selector and
the nature of plasticizer, but also relies on the structure of PANI
coating film.29 The PANI films were changed along with the
experimental conditions.
3.3.1 The effect of the reaction temperature. Different reaction temperatures have an effect on the molar mass of polyaniline. At ambient temperature and at about 0  C, the oxidation of
aniline was carried out respectively according to section 2.4. Two
different membranes were used for the electrodes and emf
measurements. The results show that the potentiometric response
characteristics have not been obviously changed by the reaction
temperature. The only difference was the response time, which
was 15 s and 20 s, respectively, based on the membrane obtained
at 0  C and room temperature.

Repeated depositions of PANI have been used to control the

thickness of the polymeric film deposited on the PVC membrane
surface. Three kinds of PANI films with different coating times
have been prepared and used for the electrodes and emf
measurements. The slopes are within the range of 58.0  0.4 mV
per decade and the detection limits are within 2.6  0.5
107 M
for the three kinds of film-based electrodes. The results indicate
that all the potentiometric responses with different thicknesses of
PANI coated membranes showed the similar near-Nernstian
behaviors and stability. The following conditions for potentiometric response were observed with a single time coating PANI
film on the PVC membrane.
3.4 pH value
PANI films were found to be sensitive to pH changes, thus it is
necessary to find the optimum pH range. The effect of pH of the
test solution (1.0
102 M MA) on the electrode potential was
investigated by following the variation in potential with change
in pH by the addition of very small volumes of phosphoric acid
and/or sodium hydroxide (0.1 M). The representative curve is
shown in Fig. 3, which indicates that the potential remained
almost constant over a pH range of 4.09.0. Therefore, the pH
range 4.09.0 was taken as the working pH range of the proposed
electrode. The observed drifts at lower pH value could be
attributed to the protonation of PANI in the coating phase and
the drifts at higher pH value could be owing to the formation of
some hydroxyl-coordinated central metal complex.
3.5 The response characteristic of the PANI-coated membrane
electrode
The analytical performance of the PANI-coated and uncoated
PVC-Mn(salen) membrane to L-mandelic acid and D-mandelic
acid were tested in the phosphate butter solution pH 7, which is
in the recommended working pH range 49 interval.
The potential responses of the PANI-coating chiral salen
Mn(III) electrode to D-MA and L-MA at various concentrations
are shown in Fig. 4. It is obvious that the different potential

3.3.2 Frequency of PANI coating. The preparation of PANI

coated membranes was performed according to section 2.4.

Fig. 2 The hydrophilicity of uncoated PVC membrane, PANI coated

membrane without ion carrier (N) and with ion carrier (C).

This journal is The Royal Society of Chemistry 2012

Fig. 3 The effect of pH dependence profile of the PANI-coating

membrane electrode in test solution (1.0
102 M MA solution).

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Scheme 1 The hydration of PANI in the presence of hydrated MA ion.

Fig. 4 The potential response characteristics of PANI-coating chiral

salen Mn(III) based electrode for D-MA and L-MA at various concentrations in the phosphate buffer solution (pH 7).

modified electrode for interfering anions relative to D-MA is 2.9,

which implies the proposed electrode is fairly enantioselective
towards L-MA over D-MA.

3.6 Mechanism of chiral recognition performance based on

PANI-coated membrane
responses are observed between enantiomers D-MA and L-MA.
The electrode exhibits excellent stereoselective recognition
toward L-MA with a slope of 57.6 mV per decade, a detection
limit of 2.1
107 M in a concentration range of 1
1061

101 M. The response time of a sensor was about 15 s for 102 and
103 M L-MA solution. The detection systems are stable and
can be used over a period of 3 months without observing
a considerable change in their response characteristics.
Compared with the uncoated membrane, Table 1 obviously
indicated that the PANI-coated membrane offers the better
response, sensitivity and the widest linear range for L-MA. The
response time was 15 s, which was faster than the uncoated
membrane. Slope and Log Kpot
l,d (by the modified separate solution
method [MSSM]) for the coated PVC-Mn(salen) membrane
sensor have a little observable difference compared with the
uncoated membrane, but the detection limit of the coated
membrane for L-MA which reached to 2.1
107 M is lower
than the uncoated membrane. Probably, in the lower concentration, the permeability of membrane for anions is stronger than
uncoated PVC membrane leading to the excellent sensitivity.
While the chiral selector plays an important role in the sensors,
which directly influence their selectivity to analytes.
Different methods of selectivity determination have been found
in the literature. In this work, the enantioselectivity coefficient
(Kpot
L-MA, D-MA) of sensor has been also evaluated using modified
form of fixed interference method ([FIM]) at 1.0
102 M
concentration of interfering ions as per IUPAC recommendation
(according to section 2.5). The selectivity was investigated in the
presence of D-MA and potentiometric selectivity coefficients of

Selective coefficient and potentiometric response slope for the

coated PVC-Mn(salen) membrane sensor have no considerable
difference compared with the uncoated membrane. However,
other important potentiometric response characteristics, such as
detection limit and linear range of the coated membrane are
better than uncoated membrane. On the one hand, the enantiorecognition ability of chiral salen Mn(III) was evaluated by
different energy and thermodynamic stabilities of complexes
formed by D-MA or L-MA coordinated to salen Mn(III).
According to literature,16 the energy of salen Mn(III)-L-MA
complex with a stable structure is 23 kJ mol1 lower than salen
Mn(III)-D-MA complex, which may explain why the electrode
based on salen Mn(III) enantioselectively responds to L-MA. On
the other hand, the increasing potentiometric response characteristics by PANI films deposition are related to ion hydration.
It is generally thought that the presence of the better hydrated
anions can weaken the local hydrogen bond network.30 It is well
known that the introduction of different anions and cations can
lead to appreciable variation in the water solubility of neutral
species.25 The capability of ions to perturb the inherent water
structure seems to be responsible for the alteration of the neutral
species hydration. This capability is certainly related to the ions
hydration characteristics. For this reason, we assume that better
hydrated anions such as MA ions can perturb the water structure
(Scheme 1). The water molecules in the presence of highly
hydrated MA anions can provide an efficient hydration of the
imine groups of the PANI chains. Stronger water-PANI interactions seem to be favorable for the transport of hydrophilic
solutes through the PANI layer.22

Table 1 The response performance of the PANI-coated and uncoated membranes

Electrode

Linear range (M)

Detected limit (M)

Response time (s)

Slope (mV per decade)

Log Kpot
l,d

Uncoated membrane16
PANI-coated membrane

1.0
105101
1.0
106101

6.5
106
2.1
107

20
15

58
57.6

4.02
4.35

810 | Anal. Methods, 2012, 4, 807811

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4. Conclusion
In the present study, we have described a novel way to design an
enantioselective, potentiometric electrode for chiral recognition.
The surface of a conventional plasticized PVC membrane was
coated with a chemically generated film of a polymer, PANI.
Based on the stereorecognition power of the active chiral salen
Mn(III) compound and stronger PANI hydration, the electrode
can be successfully used for the enantioselective analysis of L-MA
in the concentration range of 1.0
106101 M. Compared with
uncoated membrane, the electrode exhibited good sensitivity and
Nernstian response characteristics. The work will provide the
reference for the electrode improvement and the chiral hydrated
anion assay.

Acknowledgements
The authors are grateful for the financial support provided by
the Fundamental Research Funds for the Central Universities
(No. XDJK2009C091).

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