ISSN 10683755, Surface Engineering and Applied Electrochemistry, 2015, Vol. 51, No. 3, pp. 283–289.

© Allerton Press, Inc., 2015.

Pharmaceutical Electrochemistry:
The Electrochemical Detection of Aspirin Utilising
Screen Printed Graphene Electrodes as Sensors Platforms1
Senee Kruanetra, Radhakrishna Prabhub, Pat Pollardc, and Carlos Fernandezc
a
The Center of Excellence for Innovation in Chemistry and Department of Chemistry, Faculty of Science,
Mahasarakham University, Kantarawichai District, Mahasarakham, 44150 Thailand
bSchool of Engineering, Riverside East, Robert Gordon University, Aberdeen AB10 7GJ, United Kingdom
c
School of Pharmacy and Life Sciences, Riverside East, Robert Gordon University,
Aberdeen AB10 7GJ, United Kingdom
email: [email protected]
Received April 29, 2014; in final form, September 22, 2014

Abstract—A sensitive electrochemical sensor was designed for acetyl salicylic acid detection using graphene
modified Screen Printed Electrodes. The electrochemical response of the sensor with graphene was improved
compared to Screen Printed Electrodes without graphene and displayed an excellent analytical performance
for the detection of acetyl salicylic acid. The high acetyl salicylic acid loading capacity on the electrode sur
face and the outstanding electric conductivity of graphene were also discussed in this manuscript. When a
range of different concentrations of acetyl salicylic acid from 0.1 to 100 μM into a pH 4 buffer solution
(N defined as the sample size N = 9) were plotted against the oxidation peak a linear response was observed.
The detection limit was found to be 0.09 μM based on (3σ/slope). Screen Printed Graphene electrodes sen
sors methodology is shown to be useful for quantifying low levels of acetyl salicylic acid in a buffer solution as
well as in biological matrixes such as human oral fluid. A linear response was obtained over a range of con
centrations from 10 to 150 μM into a human oral fluid solution (N = 10) giving a detection limit of 8.7 μM.

Keywords: acetyl salicylic acid, electrochemical, sensor, modified Screen Printed Electrode
DOI: 10.3103/S1068375515030114

1
INTRODUCTION The utilisation of screenprinted electrodes as sen
sors platforms have attracted great interest since they
Acetylsalicylic acid (ASA) or aspirin which is provide a low cost, singleshot disposable yet highly
depicted in Fig. 1, was introduced in the late 1890s [1]
reproducible and reliable electrochemical measure
and has been used to treat a variety of inflammatory
conditions for more than 200 years. In 1763 the active ment of the target analyte [10].
ingredient of Aspirin was discovered by Edward Stone The electrochemical detection of aspirin has
from the bark of the willow. attracted great attention and different strategies have
A number of analytical approaches have been been employed. For instance Srivastava et al. [11] used
employed to analyse ASA such as: highperformance surfactantmodified multiwalled carbon nanotube
liquid chromatography–mass spectrometry [2–6] and paste electrode for the determination of ASA in phar
gas chromatography–mass spectrometry [7], ultra maceutical formulations, urine and blood samples by
performance liquid chromatography tandem mass voltammetry. Tsai et al. [12] investigated the electro
spectrometry [8] and capillary electrophoresis [9] have catalytic oxidation of acetylsalicylic acid at multi
also been reported for the determinations of ASA.
However, many of these methods require sample pre
treatment, several timeconsuming manipulation
O
steps, sophisticated instruments and special training.
In contrast, suggesting of electrochemical sensors is O
an attractive alternative method for electroactive spe
cies detection, because of its inherent advantages of O OH
simplicity, high sensitivity and relatively low cost [10].
1 The article is published in the original. Fig. 1. Chemical structure of Aspirin.

283
284 SENEE KRUANETR et al.

walled carbon nanotubealuminacoated silica nano 0.1 µM. In the same manner a stock solution of aspirin
composite modified glassy carbon electrodes. Lu et al. was prepared by dissolving the required mass in human
[13] reported an electrochemical sensor based on oral fluid to give a concentration of 1 mM. Working
AuNPs modified molecularly imprinted polymer film standards, for initial voltammetric studies, were pre
for the detection of ASA. Rynkowski et al. [14] pared by dilution of this solution with human oral fluid
reported Voltammetric studies of acetylsalicylic acid to give a final concentration of 0.1 µM.
electro oxidation at platinum electrode. These reports
showed good detection limits and sensitivity however
the main drawback is the need of extra time to modify 1.2. Electrodes
the surface of the electrode which involves various Screen Printed Graphene Electrodes (SPGrE) and
steps. Screen printed graphite electrodes (SPGE) which
Graphene has attracted a great attention since it both have a 3 mm diameter for the working electrode
discovery due to its large surface area, high thermal were obtained from Gwent Electronic Materials Ltd.
and electrical conductivities, impressive mechanical (Pontypool, Cardiff, UK). Two sets of SPE were
properties, and low cost [15, 16]. The application of employed to obtain the results. One SPE system was
graphene in sensors technologies, catalysis, nanocom composed of three electrodes with graphite as a work
posites and capacitors amongst others have increased ing and counter electrode and silver/silver chloride for
dramatically in the last decade. the reference electrode. The other system was com
Graphene sheets have extraordinary electronic posed of three electrodes with graphene as a working
transport properties and high electrocatalytic activities electrode and graphite as a counter electrode and sil
[17–19], and they have been investigated as electrode ver/silver chloride for the reference electrode.
materials in optoelectronic devices [20], electrochem
ical supercapacitors [21], fabricated fieldeffect tran 1.3. Electrochemical Measurements
sistors [22], and constructed ultrasensitive chemical
sensors [23], such as pH sensors [24], gas sensors [25], Voltammetric measurements were carried out using
and biosensors [26]. a µAutolab III (Eco Chemie, Amsterdam, The Neth
erlands) potentiostat/galvanostat and controlled by
To the best of our knowledge, there is no report Autolab GPES software version 4.9 for Windows XP.
based on using graphene modified Screen Printed The electrodes have been characterised electrochemi
Electrodes (SPGrE) for the determination of ASA. In cally and have found to exhibit a heterogeneous elec
this manuscript we proposed a simple, fast and without tron transfer rate constants of ~1.7 × 10–3 cm s–1 using
pretreatment of the electrode surface methodology in the ferrocyanide redox couple in 0.1 M KCl. The
which graphene is already printed insitu on the screen cyclic voltammetric parameters were as follows: initial
printed electrode. The electrochemical behaviors of potential of 0 V, vertex potential 1.5 V, end potential
ASA using SPE with and without graphene were also 0 V, step potential 5 mV.
investigated and discussed in this manuscript. Cyclic
Voltammetry (CV) techniques were employed in the
proposed method for the determination of ASA in 2. RESULTS AND DISCUSSION
drug preparations and human oral fluid as well as a
technique to investigate ASA electrooxidation mech 2.1. Electrochemical Characterization of SPGrE
anism. First of all we turn our attention into the investiga
tion of the SPGrE and the SPE electrodes surfaces. An
electrochemical probe containing 1.0 × 10–3 mol L–1
1. EXPERIMENTAL SECTIONS [K3Fe(CN)6] and 0.1 mol L–1 KCl was employed by
1.1. Reagents using cyclic voltammetry at a scan rate of 100 mV/s
which is depicted in Fig. 2.
All chemical reagents used to prepare solutions
were purchased in their purest commercially available The voltammograms obtained at a bare SPE (curve a),
forms from Aldrich. All aqueous solutions were made and SPGrE (curve b) are illustrated in Fig. 2. The
up with water (of resistivity of not less than 18 shape of the voltammogram shows a reversible one
MOhm cm) taken from an Elgastat filter system (Viv electron transfer process. At the bare SPE the peakto
endi, Bucks., UK). All experiments were undertaken peak separation observed is approximately of 68 mV
at 23 ± 2°C. Aspirin containing tablets of different which corroborates with the reversible redox process
pharmaceutical companies such as Galpharm Inter of [K3Fe(CN)6]. The curve a shows a voltammogram
national Ltd. were purchased from the local market. A of [Fe(CN)6]3– with peak currents at Epa (anodic peak
stock solution of aspirin was prepared by dissolving the potential) = 0.173 V and Epc (cathodic peak potential) =
required mass in buffer to give a concentration of 0.243 V respectively.
1 mM. Working standards, for initial voltammetric The current increases from 230 to 630 µA when the
studies, were prepared by dilution of this solution with SPE is modified with Gr (Fig. 2b). The dramatic peak
phosphate buffer to give a final concentration of current increase is owed to the excellent electric con

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 PHARMACEUTICAL ELECTROCHEMISTRY 285

750 b 1200
1200 1000
800

Ip, µA
500 600

Peak current, µA
a 800 400
200
Current, µA

250 400
0
0 5 10 15 20 25 30 35
Scan rate, mV/s1/2
0 0
Increasing
–250 –400 scan rates

–500 –800
0 0.1 0.2 0.3 0.4 0.5 0.6
–0.1 0 0.1 0.2 0.3 0.4 0.5
Potential, V vs. (Ag/AgCl)
Potential, V vs. (Ag/AgCl)

Fig. 2. Cyclic voltammograms response observed for Fig. 3. Cyclic voltammograms response observed for SPE
(a) a bare SPE and (b) SPE modified with Gr in 1.0 × modified with Gr in 1.0 × 10–3 mol L–1 [Fe(CN)6]3– con
10 ⎯3 mol L–1 [Fe(CN)6]3– containing 0.1 mol L–1 KCl. taining 0.1 mol L–1 KCl at different scan rates (from inner
Scan rate: 100 mV/s. to outer): 5, 10, 25, 50, 75, 100, 500 and 1000 mV/s.

duction of graphene compared to graphite. The peak buffer solution (curve b) a very sensitive anodic peak
potential is also affected by the modification of the with current of 752 mV was detected when using
electrode surface with graphene. The peak potentials SPGrE.
cathodic and anodic of graphene shifted when com
pared to the bare SPE. The values for graphene were
observed to be Epa (anodic peak potential) = 0.113 V 2.2. Electrochemical Behaviour of Aspirin
and Epc (cathodic peak potential) = 0.283 V respec 2.2.1. The effect of pH. The possible mechanism
tively, while for the bare SPE were Epa (anodic peak ASA oxidation is shown in Scheme 1. ASA in aqueous
potential) = 0.1373 V and Epc (cathodic peak poten media oxidizes to Salicylic Acid and Acetic Acid as
tial) = 0.246 V. depicted in Scheme 1. The first step of ASA electro
Cyclic voltammetry was also employed to extract oxidation visible in the voltammograms as a peak
information related to the electroactive area of the which is depicted in Fig. 5 involves an exchange of one
SPGrE compared to SPE electrode. The Randles– electron and is the ratedetermining step. The next
Sevcik equation is given by Ip = 2.69 × step, invisible in the voltammograms due to overlap
105 n3/2AD0SC0v1/2. From this equation the electroac ping with oxygen evolution, involves an exchange of
tive area could be obtained from the slope of a plot of the second electron. Assuming that these two steps
the voltammetric peak current (Ip) versus the square demand an exchange of two electrons, this indicates
root of scan rate (v1/2) which is shown in Fig. 3.
As predicted by the Randles–Sevcik equation the
700
redox peak currents at the graphenemodified SPE
increased linearly with the scan rate in the range from 600
5 to 1000 mV/s (inset, Fig. 3; linear regression equa
tion: Ip = 36.999 + 42.337v, R = 0.992). These values 500
Current, µA

indicate that the modifiedelectrode reaction is a sur

face confined process. 400

Next, in order to investigate the electrochemical 300

behaviour of ASA on a SPGrE in pH 4 phosphate b
buffer solution a CV was used. Figure 4 shows two vol 200
tammograms of the Gr modified electrode in the pres 100
ence and absence of 10 µM ASA in pH 4 phosphate a
buffer solutions at scan rate: 100 mV/s.
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
When aspirin an electroactive specie was not
present (curve a), no redox peaks were observed in the Potential, V vs. (Ag/AgCl)
potential range from 0 to 1.5 V using the SPGrE. This
Fig. 4. Cyclic voltammetric response recorded at SPE
shows that graphene was nonelectroactive in the modified with Gr (a) without 10 µM ASA and (b) dot line
scanned potential window. On the contrary when aspi with 10 µM ASA in pH 4 phosphate buffer solution. Scan
rin was present at 10 µM ASA in pH 4 phosphate rate: 100 mV/s.

SURFACE ENGINEERING AND APPLIED ELECTROCHEMISTRY Vol. 51 No. 3 2015

286 SENEE KRUANETR et al.

O O
+ H2O +
O O OH
O OH O OH
Aspirin Salycilic Acid Acetic Acid

O OH O O− O O− O O− O O− O O−

OH O• O O O O
–e––2H –e– or
• • + +

–e– –e–
H2O H2O H2O H2O
–H+ –H+

O O− O O− O O− O O−

OH OH O O
H
HO OH H OH
OH
–2e– –2e– –e– –e–
–2H+ –2H –2H –2H

O O− O O− O O− O O−

O O O O

O (a) O O (b) O

Scheme 1. Suggested mechanism of ASA electrooxidation in the pH range (a) 2–8 and (b) 8–10.

that 3 protons are possibly exchanged. If pH values are

higher than 8 (Scheme 1b), Ep and E1/2 values are
400 independent on pH. This means that protons are no
longer involved in the ASA electrooxidation. Proba
350 bly, this result from the fact, that at higher pH values,
300 hydrolysed form of ASA is already chemically depro
tonated.
Current, µA

250
The dissociation constant or pKa is an important
200 factor to consider, the pKa of ASA is reported to be
150 3.49 within the literature [27]. ASA therefore was pre
pared in a phosphate buffer solution at pH 4 where the
100 b electrooxidation of ASA will be more favourable.
50 a At pH 4, ASA is easily oxidised compared to more
basic pHs as illustrated in Figs. 6a and 6b, these values
are in agreement with ASA mechanism which is
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 depicted in Scheme 1a.
Potential, V vs. (Ag/AgCl) Figure 5a shows an irreversible voltammogram of
ASA with a relative weak redox current peak at Epa
(anodic peak potential) = 712 mV when bare SPE
were utilised. Figure 5b illustrates an irreversible volta
Fig. 5. Cyclic voltammetric response recorded at SPE (a)
without Gr and (b) dash line: modified with Gr in 10 µM mmogram of ASA on the graphenemodified SPE in
ASA in pH 4 phosphate buffer solution. Scan rate: which a welldefined oxidation peak at Epa = 752 mV
100 mV/s. is observed. This peak can be assigned to the oxidation

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 PHARMACEUTICAL ELECTROCHEMISTRY 287

160 (a) 0.80 (b)

0.78
140 0.76

Peak potential, V
Peak height, µA

0.74
120
0.72
100 0.70
0.68
80 0.66
0.64
60
0.62
40 0.60
2 4 6 8 10 12 2 4 6 8 10
pH pH

Fig. 6. (a) A plot of peak height as a function of pH for the electrochemical oxidation of 10 µM ASA using SPE modified with Gr.
Scan rate: 100 mV/s. (b) A plot of peak potential (Ep) as a function of pH for the electrochemical oxidation of 10 µM ASA using
SPE modified with Gr at Scan Rate: 100 mV/s.

of ASA to Salycilic Acid, as reported in literature [14]. ments pH 4 was chosen to be the most favourable con
The increase of the peak current in Fig. 5b compared dition to occur the electrooxidation of ASA.
to Fig. 5a can be attributed to the graphene effect.
Next, the effect of peak height current vs. pH and 2.2.2. Effect of concentration. Next, the effect of
Peak Potential vs. pH were investigated. ASA concentration on SPGrE was explored. A range
of ASA concentrations from 0.1 to 100 μM in phos
In order to investigate the effect of peak height cur phate buffer pH 4 on SPGrE was investigated using
rent versus pH the peak height current of 10 μM ASA cyclic voltammetry as indicated in Fig. 7a. Figure 7a
solution in phosphate buffer with SPGrE was mea shows the electrooxidation of ASA at height positive
sured over a solution range of pHs from 2 to 10 as illus potential +750 mV. The peak height current (Ipa) val
trated in Fig. 6a. Figure 6a illustrates that the maxi ues increases in magnitude upon the addition of ASA.
mum peak height current value for ASA in SPGrE was The ASA concentrations range from 0.1 to 100 μM
observed at pH 4 which is according to the pKa value. was plotted against the measured peak height current
This high value of peak height current indicates that (Ipa) values as illustrated in Fig. 7b. Figure 7b displays
the electrooxidation process of ASA is favourable at a good linear relationship between Ipa and ASA con
pH 4 compared to others pHs. The lowest peak height centrations. A linear regression equation was given by
value can be observed at basic pH 10 indicating that
the electrooxidation process of ASA is less favourable
which is in agreement to the Scheme 1b.
400 160
Figure 6a also illustrates a linear response over
Peak height, µA

pH 4 to pH 10 and the linear equation for that is (a) (b) 120

showed to be: Ip/μA(pH 4–10) = –11.5x + 196798 80
versus Ag/AgCl for ASA with correlation coefficients 40
Current, µA

of 0.99.
Next the effect of peak potential and pH were 0 20 40 60 80 100
200 Concentration of
investigated as it is illustrated in Fig. 6b. Figure 6b Aspirin × 10–1, µM
shows that at pH 4 there is a drop of the potential
which indicates that pH 4 is the optimum pH for the Additions
of aspirin
electrooxidation of ASA. At higher pHs the electro
oxidation process of ASA is less favourable.
The peak potential (Ep) versus pH plot is linear
(from pH 4 to pH 10) and dependent on the anodic 0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
peak potential of the analyte on the pH. The linear Potential, V vs. (Ag/AgCl)
equation can be presented by the relation:
Ep/V(pH 4–10) = 0.0075 V/pH + 0.6958 versus Fig. 7. (a) Cyclic voltammogram response observed for
Ag/AgCl for ASA with correlation coefficients of 0.99. phosphate buffer solution pH 4 at SPE modified with Gr
over a range of ASA concentrations from 0.1 to 100 µM
The above results indicated that the peak current Scan Rate: 100 mV/s. (b) A plot of peak height (Ip), as a
(Ipa) and peak potential (Epa) were affected by the pH function of ASA concentration using SPE modified with
of the solution. For the subsequent analytical experi Gr at a scan rate: 100 mV/s.

SURFACE ENGINEERING AND APPLIED ELECTROCHEMISTRY Vol. 51 No. 3 2015

288 SENEE KRUANETR et al.

160 3. CONCLUSIONS
140 It has been demonstrated for the first time the suc
120
cessful application of SPE modified with Gr towards
Peak height, µA

the electrochemical determination of ASA in an ideal

100 buffer solution as well as in a biological matrix such as
80 human oral fluid samples with excellent sensitivity and
selectivity.
60
The sensor offers a long term stability and excellent
40 reproducibility with essentially no pretreatment or
20 maintenance towards the routine analysis of ASA. A
linear response is observed for a buffered solution
0
given by the equation: (Ip/μA = 1.4079x + 15.803,
0 20 40 60 80 120 100 140 160 RI = 0.9903 and N = 9) over the range from 0.1 to
Concentration of Aspirin, µM 100 μM into a pH 4 buffer solution with a detection
limit of 0.09 μM (based on 3sigma). The determina
Fig. 8. A calibration plot of peak height (Ip), as a function tion of ASA was also linear over the concentration
of ASA concentration corresponding to the addition of range from 10 to 150 μM in a biological matrix such as
ASA into human oral fluid sample solution over the con human oral fluid. The linear regression equation is
centration range 10–150 µM using SPE modify with Gr.
Scan Rate: 100 mV/s. given by: (Ip/μA = 0.7092x + 103.92, R2 = 0.9879 and
N = 10) with a detection limit of 8.7 μM (based on
3sigma).
(Ip/μA = 1.4079x + 15.803 with N = 9, RI = 0.9903)
with a detection limit of 0.09 μM (based on ACKNOWLEDGMENTS
3σ/slope).
C.F. expresses gratitude to Robert Gordon Univer
sity and School of Pharmacy and Life Sciences for
2.3. Electroanalytical Applications financial support via a startup grant. P.P would like to
of the Proposed Method to Detect Aspirin thank the support of the IDEAS Research Institute,
in Human Oral Fluid RGU. R.P. would also like to thank the support of the
The viability of the analytical protocol was tested in IDEAS Research Institute, RGU. S.K. would like to
relation to detection within analytically relevant thank the Center of Excellence for Innovation in
media, following confirmation that successful deter Chemistry (PERCHCIC) for financial support and
mination of ASA was possible in ideal conditions util Mahasarakham University for facilities.
ising a standard pH 4 phosphate buffer.
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