Journal of the Taiwan Institute of Chemical Engineers 66 (2016) 3342

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Journal of the Taiwan Institute of Chemical Engineers

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

Electrocatalytic effect of uoroapatite in reducing paracetamol at

carbon paste electrode: Analytical application
Y. EL Bouabi a, A. Farahi a,b, M. Achak c, M. Zeroual a, K. Hnini a, S. El Houssame a,
M. Bakasse d, A. Bouzidi a, M.A. El Mhammedi a,
a
Univ Hassan 1, Laboratoire de Chimie et Modlisation Mathmatique, 25 000 Khouribga, Morocco
b
Universit Ibn Zohr, Facult de Sciences, BP 8106 Cit Dakhla, Agadir, Morocco
c
Ecole Nationale des Sciences Appliques, Laboratoire des Sciences de lIngnieur Pour lEnergie, Universit Chouaib Doukkali, El Jadida, Morocco
d
Laboratoire de Chimie Organique Bioorganique et Environnement, Facult de Sciences, Universit Chouaib Doukkali, Morocco

a r t i c l e i n f o a b s t r a c t

Article history: A carbon paste electrode modied with uoroapatite (FAPCPE) was examined to catalyze the electro-
Received 13 December 2015 chemical reduction of paracetamol (PCT). The FAPCPE has demonstrated an ecient performance to-
Revised 26 May 2016
ward PCT reduction compared to that obtained using unmodied carbon electrode. The electrochemical
Accepted 15 June 2016
behavior of PCT has been investigated and the optimum experimental conditions were achieved. More-
Available online 29 June 2016
over, a good linear relationship was achievable over the concentration range from 4.0 108 mol/L to
Keywords: 1.0 103 mol/L using square wave voltammetry (SWV). The detection limit (S/N = 3) was also calculated
Fluoroapatite and a low value of 1.25 108 mol/L was obtained with 210 s of accumulation time. The effect of coex-
Square wave voltammetry isting of interferent compounds such as ascorbic acid (AA), citric acid (CA) and a binary mixture with
Paracetamol dopamine (DA) was also investigated. The proposed method was successfully applied to PCT determina-
Water tion in natural waters, tablets and urine samples with the results agreeing with independently veried
Tablets
HPLC.
Urine
2016 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction
Drug analysis plays a major role in the quality control of drug
formulations which has great health risks. A simple, sensitive and
accurate method to determine the active ingredients in drugs
seems essential [1].
Paracetamol (acetaminophen) is one of the important drug hav-
ing antipyretic and analgesic properties most frequently prescribed
throughout the world. It has been proved to be extremely e-
cient for the mild pain relief, muscular aches, neuralgia, migraine
headache, rheumatic pain, fever and osteoarthritis [2].
In general, PCT seems to be safe and appears to have no toxic
effects on humans health when taken in normal therapeutic doses
[3]. However, taking high doses of PCT may cause adverse effects in
the body, although in proper doses it does not display any side ef-
fects. Nowadays, PCT is widely used for its remarkable therapeutic
characteristics thus precise determination and control of its quality
is vital [4].
Corresponding author. Tel.: +212 68858296; fax: +212 23485201.
E-mail address: elmhammedi@yahoo.fr, elmhammedi@gmail.com (M.A. El
Mhammedi).
The review of literature for the assessment of PCT either indi-
vidual or in combined dosage form reveals that a number of meth-
ods have been reported based on various analytical techniques.
Those established methods include capillary electrophoresis (CE)
[5], high performance liquid chromatography (HPLC) [68], HPLC-
tandem mass spectrometry [9], TLC [10], UV-spectrophotometry
[11,12], titrimetry [13], spectrouorometry [14], colorimetry [15],
Fourier transform infrared spectrometry [16] and thermogravimet-
ric analysis (TGA) [17]. However, although the analysis of PCT has
been extensively studied, to our knowledge few works based on
electrochemical methods using modied electrodes have been de-
veloped [1820]. In addition, the electrochemical methods are very
simple, highly sensitive and low apparatus cost than other tradi-
tional methods [21]. It is noteworthy, that the modied electrodes
show a high sensitivity and selectivity toward the determination of
PCT [22,23] than the unmodied ones [24].
The low biodegradability of PCT motivates us to develop the re-
dox methods favoring its electrochemical activity. Indeed, the elec-
trocatalytic reduction or oxidation can be advantageously applied
to the extensive treatment of real matrices to detect and eliminate
PCT. Consequently, a suitable catalyst is of great interest in real ap-
plications and it can be used to accelerate the reduction of PCT
with a signicant increase of the reduction currents and a shift of
potentials towards less negative values.

http://dx.doi.org/10.1016/j.jtice.2016.06.013
1876-1070/ 2016 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
34 Y. EL Bouabi et al. / Journal of the Taiwan Institute of Chemical Engineers 66 (2016) 3342
Fig. 1. (A) CVs of 1.0 104 mol/L PCT on the (a) CPE and (b) FAPCPE at scan rate of 50 mV/s in 0.1 mol/L PBS (pH 7.0). (B) Square wave voltammograms of 1.0 104 mol/L
PCT in 0.1 mol/L PBS at (a) CPE and (b) FAPCPE (FAP/CP of (6/4: w/w).
Continuing with our interest in the use of uoroapatite (FAP) as
a carbon paste modied electrodes having sensing probes toward
the oxidation or reduction of various electroactive species [25,26].
Among the different inorganic solids, FAP has advantages because
it is cheap, readily available, stable in water, non-toxic, not a pollu-
tant and, in particular, the uorapatite is reputed unanimously for
their weak solubility [27], herein we report an ecient and per-
tinent method for the electroreduction of PCT using square wave
voltammetry. This methodology has been successfully applied to
construct an enhanced sensing platform for the electrochemical
detection of PCT in natural water samples, commercial tablets and
human urines without any sample pre-purication steps.
2. Experimental
2.1. Reagents
All chemicals used were of analytical grade or of the high-
est purity available. FAP [28], sodium hydroxide, sodium phos-
phate dibasic, monosodium phosphate and chloridric acid were
purchased from commercial sources and used as received.
Paracetamol (Malinkroute, 99.99%) was dissolved in phos-
phate buffer solution (0.1 mol/L) to prepare stock solutions of
1.0 103 mol/L. Then the working standard solutions were pre-
pared by successive dilution of the stock solutions by sodium sul-
fate. Carbon paste was supplied from Carbone, Lorraine, ref 9900,
France. All the reagents used were of analytical grade. Distilled wa-
ter (DW) was used throughout the preparation of the solutions.
2.2. Instrument
Electrochemical measurements were carried out by using an
eDAQ e-corder/potentiostat EA163 controlled by eDAQ EChem data
acquisition software and equipped with three electrode system
mounted on cell. Working electrode was FAP-modied carbon
paste electrode, the counter electrode was a platinum plate and
Ag/AgCl/Cl (3 mol/L) served as reference. The pH-meter (Ra-
diometer, sensIONTM , PH31, Spain) was used for adjusting pH
values.
The electrochemical impedance measurements were done via
an electrochemical impedance analyzer potentiostat (model PGZ
100, Eco Chemie B.V., Utrecht, The Netherlands) using a computer
controlled by voltalab master 4 software logiciel.
2.3. Preparation of the chemically modied electrode
The modied carbon-paste electrode was prepared by mixing
the graphite powder with the uoroapatite to give a ratio FAP/CP
of (6/4 : w/w). Portions of the resulting composite material were
then packed into a home built electrode assembly consisting of the
cavity (geometric area 0.1256 cm2 ) of PTFE cylindrical tube elec-
trode of a plastic pipette tip. Electrical contact was established
with a bar of carbon.
2.4. Electrochemical measurements
A glass cell was washed with 10% hydrochloric acid then rinsed
with DBW. Two-step procedures were followed for the analyt-
ical determination of PCT in aqueous samples. At open circuit,
the working electrode was rst immersed in 0.1 mol/L phosphate
buffer solution (PBS) containing PCT. Where the accumulation of
PCT was achieved chemically, the square wave experiments were
performed in PBS electrolyte solutions at FAPCPE. The potential
range was performed from 0.0 mV to 500 mV with a frequency of
30 Hz, pulse height of 40 mV and modulation amplitude 5 mV at
scan rate 150 mV/s. The cyclic voltammogram was recorded be-
tween 0.4 and 1.0 V. EIS was performed between 100 kHz and
100 mHz at AC amplitude of 10 mV. All measurements were per-
formed at room temperature.
2.5. HPLC analysis of paracetamol
The chromatographic separation was applied using a mobile
phase of water and methanol (20/80), through a Nucleosil 100-
5 C18 (250 4.6 mm I.D. 5 m) column (Macherey-Nagel, Ger-
many), with an injection volume of 10 l, and a ow rate set to
1.0 mL/min. The detector responses were measured in terms of
peak area, using the Borwin chromatographic software for storage,
and data mining process.
3. Results and discussion
3.1. Electrocatalytic behaviors of PCT at FAPCPE
3.1.1. Comparisons between CPE and FAPCPE
The electrochemical response of 1.0 104 mol/L PCT in
0.1 mol/L phosphate buffer (pH 7) at the working electrodes have
been studied by using cyclic voltammetry (Fig. 1A). On the unmod-
ied CPE (Fig. 1Aa), PCT shows a quasi-reversible redox. In the case
 Y. EL Bouabi et al. / Journal of the Taiwan Institute of Chemical Engineers 66 (2016) 3342
Fig. 2. CVs of 1.0 104 mol/L PCT on FAPCPE at different scan rates (1, 5, 10, 50, 100, 160, 200, 250 and 320 mV/s) in 0.1 mol/L PBS (pH 7.0). Inset, the plot of the peak
current vs. scan rate.
of FAPCPE, a pair of well-dened and reversible redox peaks cor-
responding to the electrochemical reaction of PCT was obtained,
with Epa = 446 mV and Epc = 330 mV. It can be seen that the re-
duction over potential of PCT becomes higher than that on CPE
with a positive shifting of 314 mV. An Epa shifted toward nega-
tive potentials in the presence of the uoroapatite (Fig. 1Bb) was
shown. The results demonstrated that the electrochemical reactiv-
ity of PCT is remarkably improved on the FAPCPE. Owing to its
high adsorptivity and good biocompatibility, FAP particles effec-
tively modify the surface chemistry of carbon, which provides an
ecient interface and microenvironment for the electrochemical
reaction of PCT.
Results conrm that the FAP can catalyze paracetamol oxida-
tion, this was possible thanks to their structure, the presence of
Brnsted acid sites and Lewis and their ability to make exchanges
ion. In the square wave voltammetric, the oxidation peak currents
of paracetamol on the FAPCPE were about 80 fold higher than
that of the unmodied electrodes (Fig. 1B).
3.1.2. Effect of scan rate
The scan rate effect on the anodic and cathodic peak current
of PCT on the FAPCPE was investigated. As shown in Fig. 2, the
anodic and cathodic peak currents increase as the scan rate grows
from 5 to 250 mV/s. The linear relationship between the peak cur-
rent and square root of scan rate can be expressed by the linear
regression equations as: Ipa/A = 8.16(v)1/2 12.62 (R = 0.982) and
Ipc/A = 2.39(v)1/2 4.30 (R = 0.988), respectively. According to
the literature, the results indicate that the electrochemical reaction
of PCT on the FAPCPE is a surface-controlled process [29,30]. In
addition, Epc is shifted to positive potentials, while Epa is neg-
35
atively shifted. This can be due to changes in the electroactivity
and kinetic effect of FAPCPE surface on the reduction of PCT
especially at scan rates lower than 5 mV/s. In other words, at scan
rates lower than 5 mV/s the time window for the PCT oxidation
becomes very narrow, avoiding the facile electron transfer between
substrate and catalytic sites.
At high scan rates ranging from 1 to 320 mV/s, plotting the
Epa and Epc vs. lnv produces a straight line with the linear re-
gression equations as: Epa = 0.032 ln(v) + 0.276 (R = 0.958) and
Epc = 0.027ln(v) + 0.475 (R = 0.996), respectively. According to
Lavirons equation [31], the slops of the lines are equal to RT/ nF
and RT/ nF, respectively. Therefore, the electron transfer coe-
cient ( ) and the electron transfer number (n) are calculated to be
0.54 and 2, respectively. The adsorbed amount of PCT on the sur-
face of FAPCPE was further calculated by the following equation:
ip = n2 F2 A v/4RT [31]. Based on the relationship of ip with v, the
value of the surface concentration of the PCT () was obtained with
the results as 4.54 108 mol/cm2 . This high surface concentration
can be attributed to the FAP modier.
3.1.3. Effect of pH
Fig. 3 represents CVs of the modied electrode in
1.0 104 mol/L PCT at various pH values. A decrease in pH
of the solution from 12.0 to 2.0 led to a positive shift in both
reduction and oxidation peak potentials. So the peak potentials
seem to be affected by the concentration of H+ , suggesting the
presence of protonation step in the electrochemical mechanism
as indicated in Schema 1. However, there was no considerable
decrease in the peak currents. These results indicated that the
slope was 45.0 0.65 mV/pH over a pH range of 2.0 to 12.0. This
36 Y. EL Bouabi et al. / Journal of the Taiwan Institute of Chemical Engineers 66 (2016) 3342

Fig. 3. CVs of FAPCPE at different pH values: 2.012.0; 1.0 104 mol/L in 0.1 mol/L PBS; Plot of Epc vs. pH value.

O O used to evaluate the electrocatalytic effect of the uoroapatite.

Fig. 4 represents the current-time proles obtained by setting the
HN C CH3 N C CH3 working electrode potential. As seen, the behavior is typical of that
expected for a mediated reduction. We found that cathodic cur-
rent of the PCT on FAPCPE is still higher than that measured on
- 2H+ the unmodied carbon paste electrode, indicating that electrode
FAPCPE has high catalytic ability to reduce PCT. This conrms
- 2e-
the results previously obtained by cyclic voltammetry. The perfor-
mance of PCT reduction on the FAPCPE reached 50% compared to
CPE. The results obtained by chronoamperometry, show that elec-
O
OH trode FAPCPE can effectively catalyze the reduction of PCT.

Schema 1. Proposed mechanism of PCT reduction. 3.3. Electrochemical impedance spectroscopy studies

Fig. 5 shows Nyquist plots of 1.0 104 mol/L in the 0.1 mol/L
value was smaller than the ideal Nernsts value of 59.2 mV/pH for
PBS at these electrodes within the frequency range of 100 kHz to
a two electron and two proton process [32]. According to the lit-
100 mHz at the formal potential of the redox probe. The almost
erature, we can predict that the mechanism depicted in Schema 1,
straight line plots obtained implies the low charge transfer resis-
seemed to be proposed for the reduction of PCT [3336]. This
tance of the redox probe [39,40]. At high frequencies, CPE (curve a)
behavior is due to the contribution of H+ ions and the structural
experiences a sharp increase of Zim and behaves closer to an ideal
changes in OH and NHCOCH3 groups of PCT which get in-
capacitor [41]. The presence of a small and depressed semicircle in
volved in the reduction process of paracetamol [37,38]. Therefore,
curve (b) at lower frequencies could be due to the charge-transfer
pH 7.0 was selected as the optimum pH for the electrochem-
resistance (Rct) of the electrodes. The FAPCPE has a higher Rct
ical determination of PCT, which is close to the physiological
which implies that the interfacial resistance has increased. This re-
conditions.
sult explains the xation of the paracetamol onto electrode surface.

3.2. Chronoamperometry studies of PCT at FAPCPE 3.4. Electroanalytical studies of PCT at FAPCPE

To conrm the results obtained by cyclic voltammetry, the In order to quantify PCT, experimental conditions has been op-
chronoamperometry as another electrochemical technique was timized using the relationships between peak current (IP) and the
 Y. EL Bouabi et al. / Journal of the Taiwan Institute of Chemical Engineers 66 (2016) 3342
Fig. 4. Chronoamperograms obtained of PCT at different reduction potential, 1.0 104 mol/L in 0.1 mol/L PBS.
Fig. 5. Impedance spectra at 0 V (a) CPEPCT and (b) FAPCPEPCT.
chemical and electrochemical parameters. All these parameters ex-
ert an intense effect on the peak current. An increasing of the
pulse height from 10 to 70 mV led to the increase of peak currents
of PCT. However, after 40 mV, it caused peak broadening. Therefore,
a value of 40 mV was chosen as optimal pulse height for further
studies.
The inuence on the frequency of the current intensity of PCT
was evaluated in the range of 5 to 40 Hz (Fig. 6). The signal in-
creases with the increase of the frequency. Thus, in further ex-
periments a value of 30 Hz, corresponds to 0.033 s of duration for
each step, was employed to ensure the maximum diffusion of the
electro-active species to electrode surfaces. We can assume that
37
the redox process involves the adsorption as the rate-determining
step [42]. This behavior is typical of the responses obtained at
electrodes, where the electroactive species interact with working
electrode, in the adsorption process, before the redox reaction oc-
curs. The results conrm those obtained by varying the scan rate
in cyclic volammetry.
We have also investigated the amplitude inuence in the range
from 1 to 15 mV. The results obtained demonstrated that a height
of PCT peak increased linearly as a consequence of the increase
in amplitude values up to 5 mV. In agreement with the high peak
current values, good shapes of the signal and better signal to noise
ratio were obtained, the selected optimal values were 30 Hz, 40 mV
and 5 mV for frequency, modulation amplitude and pulse height
respectively.
The effect of pH on the determination of PCT in PBS solution
at the FAPCPE was carefully investigated in the pH range of 3.0
8.0. The anodic peak current of PCT increases with increasing pH
values until the pH reaches 6.87.0, the anodic peak current then
decreases with further increases in the pH. The maximum anodic
peak current appeared at pH 7.0. Therefore, PBS with a pH of 7.0
was selected for all subsequent electrochemical PCT analyses.
Accumulation time is an important parameter for SWV tech-
nique and has a non-negligible inuence on the sensitivity of de-
termination of PCT (Fig. 6). It is clear that the anodic peak intensity
increased with the increase of the preconcentration times in the
range from 10 s to 600 s, the anodic peak current decreased signif-
icantly around 210 s after saturation of electrode surfaces. Taking
account of sensitivity and eciency, accumulation time was 210 s
in the following experiments.
The square wave voltammograms (Fig. 6) demonstrated that the
increase of the concentration of uoroapatite as modier (from 10
to 80% by weight of carbon paste), affects the electrochemical be-
haviors of PCT at the carbon paste electrode. The peak currents
38 Y. EL Bouabi et al. / Journal of the Taiwan Institute of Chemical Engineers 66 (2016) 3342
Fig. 6. Inuence of the experimental variables (pulse height, amplitude, frequency, pH, time preconcentration and Percentage FAP/CP) involved in the SWV method and
response to PCT 1.0 104 mol/L in 0.1 mol/L PBS at the FAPCPE.
of PCT increase with the increase of the modier amount. More-
over, the intensity of peak decreases if the concentration of modi-
er is higher than 60% of FAP loading by weight (w/w). This result
is probably due to the decrease in the modied electrode conduc-
tivity. In the course of the study, a modier concentration of about
60% of the ratio FAP/CP is used.
3.5. Linear range and detection limit
The calibration curve for the SWV peak current for PCT
oxidation vs. PCT concentration shows excellent linearity over
a wide concentration range from 1.0 103 to 4.0 108 mol/L
(Fig. 7). It can be seen that the calibration plots of peak cur-
rent vs. concentration of PCT show two linear dynamic ranges
from 1.0 103 4.0 105 mol/L and 2.0 105 4.0 108 mol/L
(Fig. 7). The linear regression equations for these two re-
gions are ipa(A) = 0.037 [PCT] (mol/L) + 124.1 (R = 0.977) and
ipa(A)=3.238[PCT] (mol/L) + 25.73 (R = 0.990).
The standard deviation of the mean current (sb) measured at
the oxidation potential of paracetamol for 10 voltammograms of
the blank solution in pure electrolytes was used [43] in the deter-
mination of the quantication limit (LOQ, 10 s) and the detection
limit (LOD, 3 s) together with the slope of the straight line of the
analytical curves. The limit of detection (DL) and limit of quanti-
cation (QL) are calculated to be respectively 1.25 108 mol/L and
4.16 108 mol/L. The precision (n = 8) assessed as relative stan-
dard deviation (R.S.D.) were 1.24% for 1.0 106 mol/L and 1.07%
for 4.0 106 mol/L, respectively. The electrochemical behavior of
FAPCPE for PCT was contrasted with some of the previously re-
ported electrodes (Table 1). It is obvious that PCT at FAPCPE
showed a low relative standard deviation, broad linearity range,
and a low detection limit.
The FAPCPE electrode here could maintain its activity as a
sensor for parectamol during 4 months; the response was 97.15%
of its initial value which shows long-term stability and very good
sensitivity for the analysis of paracetamol.
3.6. Effect of interferents
In order to evaluate the selectivity of the prepared sensor, the
effect of various possible interferents on the determination of PCT
was examined, and the results were summarized in Table 2. It
was observed that Na+ , Mg2+ , Ca2+ , Cu2+ , Pb2+ , Cd2+ , K+ , Ni2+ ,
Co3+ , Zn2+ , Al3+ , Fe3+ , Fe2+ , V5+ , Cr3+ , NO3 , showed no ob-
vious interference for the determination of 1.0 105 mol/L PCT
even when present 100 times in excess, with deviations below 4%.
However, Ag+ was found to affect the detection of PCT. It was
found that 100-fold of Ag+ interfered with the determination of
1.0 105 mol/L PCT (peak current change 5.83%). The inuences
of the presence of organic elements on the PCT signals were also
tested. At the same concentration, ascorbic acid, citric acid, ibupro-
fen and dopamine had no apparent effects on the current response
of PCT (2%). Electrochemically active ascorbic acid (vitamin C) is
often combined with PCT based drugs. No signicant interference
effect was observed in the developed SWV method up to 10 fold
concentration of ascorbic acid (Ep 200 mV) in comparison with
concentration of PCT (Ep +400 mV). As in the case of ascorbic
acid, no signicant interference effect of dopamine (Ep +200 mV)
was observed under the same conditions. Both these results in-
dicate the possibility of eventual determination of PCT simultane-
ously with ascorbic acid or dopamine.
3.7. Practical application
In order to evaluate the performance of FAPCPE by practical
analytical applications, the determination of PCT was carried out in
 Y. EL Bouabi et al. / Journal of the Taiwan Institute of Chemical Engineers 66 (2016) 3342 39

Fig. 7. SWV curves of different concentrations of PCT in 0.1 mol/L PBS (pH 7) at FAPCPE: 1.0 103 4.0 105 mol/L and 2.0 105 4.0 108 mol/L.

Table 1
Comparison of the electrochemical behavior of PCT at FAPCPE with some of the previously
reported electrodes.

Methods Linear range (mol/L) DL (mol/L) DSR (%) Refs

6
Cu-PTTCA/GCE 2050 0 0 5.0 10 [44]
VCPTE 0.1205800 88.0 106 [45]
Naon/GCE 50500 17.0 106 [46]
GCE 21580 19.0 106 [47]
CILE 1.020 0 0 0.3 106 [48]
C60/GCE 501500 0.5 104 [49]
PANI-MWCNTs/GCE 1100 2.5 107 3.9 [50]
CNi/GCE 2230 6.0 107 1.1 [51]
PAY/nano-TiO2 /GCE 12120 2.0 106 [52]
FAP-CPE 10 0 04.0 0 and 2000.04 1.25 108 1.07 Present work

Cu-PTTCA/GCE: Cu-poly terthiophene carboxylic acid modied glassy carbon electrode.

VCPTE: Vaseline carbon paste tissue electrode.
Naon/GCE: Naon modied glassy carbon electrode.
GCE: Glassy carbon electrode.
CILE: carbon ionic liquid electrode.
PAYnano-TiO2 /GCE: poly(acid yellow 9)/nano-TiO2 modied glassy carbon electrode.
C60/GCE: C60-modied glassy carbon electrode.
PANI-MWCNTs/GCE: A polyanilinemulti-walled carbon nanotubes (PANIMWCNTs) composite
modied electrode.
CNi/GCE: A novel type of carbon-coated nickel magnetic nanoparticles modied glass carbon
electrodes.
40 Y. EL Bouabi et al. / Journal of the Taiwan Institute of Chemical Engineers 66 (2016) 3342

Table 2
Inuence of coexisting substances on the determination of 1.0 104 mol/L PCT (n = 3).

Coexisting substance Concentration (mmol/L) Change of peak current (%) Coexisting substance Concentration (mmol/L) Change of peak current (%)

+ 3+
Na 1 1.27 Al 1 0.45
Mg2+ 1 1.65 Fe3+ 1 0.56
Ca2+ 1 1.89 Fe2+ 1 0.67
Cu2+ 1 1.20 V5+ 1 1.52
Pb2+ 1 1.48 Cr3+ 1 0.22
Cd2+ 1 1.47 NO3 1 1.27
K+1 1 0.85 Ibuprofen 0.1 0.40
Ni2+ 1 0.55 Ascorbic acid 0.1 1.72
CO2+ 1 0.28 Citric acid 0.1 1.5
Zn2+ 1 1.42 Dopamine 0.1 1.06
Ag+ 1 5.83

Fig. 8. Curves calibration of the determination of PCT in: (a) seawater (b) river water.

Table 3
Determination of PCT in water samples and human urines.

(FAP-CPE) (HPLC)
5 5
Samples PCT Added (10 mol/L) PCT found (10 mol/L) Recovery (%) PCT found (105 mol/L) Recovery (%)

River water 2 1.94 97.00 9.45 1.96 98.00

River water 4 3.96 99.00 5.74 3.99 99.75
Sea water 2 1.92 96.00 11.31 1.98 99.00
Sea water 4 3.95 98.75 6.41 3.97 99.25
Human urines 2 1.90 95.00 12.58 1.95 97.50
Human urines 4 3.92 98.00 8.08 3.94 98.50
Human urines 6 5.91 98.50 7.01 5.99 99.83

All samples were analyzed using standard addition method (n = 3).

Extended DPV-recovery (R) = (R0 (1 R0 )/n (n = 3), where R0 is the percentage recovery, t is a distribution value chosen for the desired
condence level. Theoretical values at 95% condence limits: t = 2.78.

real samples (river water, seawater, commercial tablets and human
urines).
(i) River water and seawater
The experiments were carried out by adding a known amount
of PCT to the support electrolyte followed by standard additions
(ii) Determination of PCT in urine samples
from the PCT stock solution and plotting the resulting analyti-
cal curve. The support electrolytes were prepared by addition of
0.1 mol/L of PBS to a fresh water samples. The plot of peak currents
against PCT concentration was linear (Fig. 8). The results of the de-
termination of PCT using calibration curves are given in Table 3. No
interference of the matrix components was observed even without
any sample pretreatment. No signal for PCT was observed when
the water samples were analyzed, which may be attributed to that
no PCT is in water samples or the concentration of PCT is lower
than the detection limit.
FAPCPE is investigated for the measurement of PCT in three
human urine samples. The percentage of recovery of the spiked
sample is in the range between 98.00 and 98.50. The results ob-
tained by this method agreed with those by the HPLC. The result
 Y. EL Bouabi et al. / Journal of the Taiwan Institute of Chemical Engineers 66 (2016) 3342
Table 4
Determination results of PCT in tablets by FAPCPE (n = 5).
(FAPCPE)
Sample Label (mg/tablet) PCT found (mg/tablet)
Doliprane 10 0 0 980
Panadol 500 489
in Table 3 was mean value of replicating measurement of three
times. Model human urine samples were used to demonstrate that
matrix components do not interfere with PCT determination. The
results show that the modied electrode is suitable for the deter-
mination of PCT in biological uids
(iii) Determination of PCT in formulation tablets
The developed method was applied to the analysis of two dif-
ferent commercial tablets. The tablets were weighed, ground into
powder, and then dissolved in 0.1 PBS mol/L adequately. All the
sample solutions were transferred to 25 mL ask and diluted with
PBS (pH 7.0). The mean percentage recoveries of added PCT were
found to be 97.80% and 98.00% using the proposed method and
HPLC, respectively (Table 4). There were no signicant differences
between the recoveries calculated at the 95 % condence level and
within an acceptable range error of 5%. The excellent average re-
coveries of formulation tablets samples suggest that the FAPCPE
developed in this work has practical signicance and is able to de-
termine PCT in formulation tablets.
4. Conclusion
A highly advanced and sensitive FAPCPE toward PCT reduc-
tion has been disclosed. The performances of FAPCPE were sig-
nicantly better than those of CPE because it exhibited a re-
markably enhanced electrocatalytical activity toward the sensing
of PCT. The inuence of the experimental variables which involved
in the SWV determination of PCT was investigated. Analytical re-
sults show that the proposed modied electrode was able to de-
tect 1.25 108 mol/L of PCT with good sensitivity and repeatabil-
ity. Results of voltammetric determination of PCT in real samples
were in good agreement with those of HPLC methods proving that
FAPCPE offers a useful and reliable method for the quantication
of PCT in real samples.
Acknowledgments
The authors wish to express their appreciation to the Hassan
1er University. This study could not have been conducted without
their nancial supports.
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