Diamond & Related Materials 43 (2014) 5–11

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Diamond & Related Materials

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Electrochemical determination of adrenaline in human urine using a

boron-doped diamond film electrode
Jozef Sochr, Ľubomír Švorc ⁎, Miroslav Rievaj, Dušan Bustin
Institute of Analytical Chemistry, Faculty of Chemical and Food Technology, Slovak University of Technology in Bratislava, Radlinského 9, Bratislava SK-812 37, Slovak Republic

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

Article history: A simple and sensitive square-wave voltammetric method for the determination of adrenaline on unmodified
Received 7 May 2013 boron-doped diamond film electrode was developed. Adrenaline exhibited the quasi-reversible behavior with
Received in revised form 16 June 2013 oxidation peak on the forward scan at +0.75 V and smaller reduction peak on the reverse scan at −0.10 V vs.
Accepted 9 January 2014
Ag/AgCl electrode in 0.5 M HClO4. The effect of supporting electrolyte, pH and scan rate on the current response
Available online 15 January 2014
of adrenaline was examined to select the optimum experimental conditions. At optimized square-wave
Keywords:
voltammetric parameters (amplitude of 100 mV, frequency of 50 Hz and step potential of 5 mV), the linear con-
Adrenaline centration range from 0.7 to 60 μM (R2 = 0.998, number of measurements n = 6), the excellent repeatability
Oxidation (relative standard deviation of 3.5% for n = 50) and the detection limit of 0.21 μM were achieved without any
Square-wave voltammetry chemical modification and pretreatment of working electrode. The practical application of method was
Detection limit demonstrated in the determination of adrenaline in spiked human urine samples with satisfactory recoveries
Human urine (98 to 102%).
© 2014 Elsevier B.V. All rights reserved.

1. Introduction Different analytical methods for the determination of ADR have

Adrenaline (also known as epinephrine, ADR) is a hormone and
neurotransmitter representing the most important catecholamine
(together with noradrenaline) produced by adrenal glands. Despite
the many positive functions of ADR in human system such as regulator
of the blood pressure, heart rate and glycogen metabolism as well as
bronchodilator for asthma, its presence may also signify a serious prob-
lem with negative impact on public health [1]. ADR is usually released
during physical (muscular exercise, thermal burn) or emotional (trau-
ma) stress which may activate the sympatho-adrenal system followed
by an increase of concentration of ADR in blood and urine. Currently,
many life phenomena such as increase of incidence and development
of cancers are related to the presence of ADR in blood at which its con-
centration usually varies from 0 to 5 nM [2,3]. The low concentration
levels of ADR have also been found in patients with Parkinson's disease
[4]. On the other hand, not only stress, but also many foods including
coffee, tea, bananas, chocolate and citrus fruits and certain drugs can
increase the concentration of ADR in urine where its content usually al-
ters in the range of 1–1 µM. Therefore, the analysis of ADR and other cat-
echolamines in biological fluids plays a significant role in the study of its
physiological functions or diagnose of some diseases in clinical chemis-
try. In respect of these objectives, there is a growing need for continual
development of novel, simple and sensitive analytical methods in re-
search and clinical laboratories.
⁎ Corresponding author. Tel.: +421 2 59325302; fax: +421 2 59325590.
E-mail address: lubomir.svorc@stuba.sk (Ľ Švorc).
been reported. High performance liquid chromatography (HPLC)
[5–7], capillary electrophoresis [8,9] and spectrophotometric [10]
techniques are among popular analytical methods for quantification
of ADR and other catecholamines. However, these methods suffer
from some disadvantages such as high cost, long analysis time and
requirement for sample pretreatment when some procedures as deriv-
atization, extraction and purification are usually included as well as de-
mands for highly skilled personnel often restrict their use in routine
analytical practice.
Electrochemical methods have many inherent advantages such as
simplicity, low cost, and possibility of miniaturization and sometimes
may represent an independent alternative to so far dominant spectropho-
tometric and chromatographic techniques. Many papers dealing with
electrochemical determination of ADR individually or simultaneously
with other drugs have been reported. These methods involve the
amperometry as a detection technique in HPLC [11–16] and enzyme
biosensors [17,18]. Nevertheless, the electrode surfaces covered by mis-
cellaneous type of modifiers such as carbon nanotubes [19–24], polymers
[25–30] or platinum [31,32] and gold nanoparticles [27,33,34] as well as
the use of microbial biosensor [35] are among the most dominating
electrochemical tools for the determination of ADR. Hence, they
have appeared to be the sensitive sensors mainly due to good elec-
tron transfer ability. Regarding unmodified (bare) carbonaceous
electrodes, carbon fiber ultramicroelectrode [36] and glassy carbon
electrode [37] have merely been utilized for the determination of
ADR. However, an irreversible adsorption of products of electrode
reaction resulting in the passivation layer usually occurs in such
electrochemical measurements.

0925-9635/$ – see front matter © 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.diamond.2014.01.005
6 J. Sochr et al. / Diamond & Related Materials 43 (2014) 5–11
Boron-doped diamond film (BDDF) as the new perspective
carbon-based electrode material opens new possibilities of electro-
chemical investigations due to its excellent features such as low ad-
sorption pertinent to sp3 character of diamond carbon, low and
stable background current, good mechanical robustness, stability in
several media and the widest usable potential window among all
electrode materials (up to 4 V) [38]. These properties are commonly in-
duced by morphologic factors, crystallographic orientation and presence
of impurities (non-diamond sp2 carbon) which make an unmodified
(bare) BDDF electrode surface significantly different from those of other
conventional carbon electrodes, e.g. glassy carbon or carbon paste.
Moreover, the physical and chemical properties of BDDF electrode are
affected by surface termination (H- and O-terminated surfaces with
high and low conductivity, respectively) [39]. The development of new
electrochemical methods using BDDF electrode can provide the invalu-
able services in drug monitoring in terms of protection of human health.
The recent reports of our working group have revealed that several
drugs such as caffeine [40], paracetamol [41], penicillin V [42] and codeine
[43] are able to be sensitively and selectively determined using unmodi-
fied BDDF electrode.
This paper describes an application of unmodified BDDF elec-
trode as sensitive electrochemical sensor for the determination of
ADR. Moreover, to the best of our knowledge, no published report
dealing with this topic using BDDF electrode is available until now
according to the literature survey. The practical usefulness of pro-
posed method is demonstrated in the determination of ADR in
spiked human urine samples. The developed procedure could also
find an application in drug monitoring thanks to rapidity, simplicity
and sensitivity.
2. Experimental
2.1. Chemicals
ADR standard (CAS No. 51-43-4, purity of 99%), urea, ascorbic acid,
uric acid, folic acid, glucose and barbituric acid were obtained from
Sigma-Aldrich (Slovak Republic) and used as received without any
further purification. The studied supporting electrolytes were acetate
buffer solution, hydrochloric acid, nitric acid, sulfuric acid and perchloric
acid (Lachema Brno, Czech Republic). All other chemicals were of
analytical grade purity. Stock standard solution of ADR (1 mM) was
prepared by dissolution of its solid standard in 5 mL of methanol and
then diluted with double-distilled deionized water with resistivity
above 18 MΩ cm. Working and calibration solutions of lower concentra-
tions of ADR were freshly prepared by diluting with supporting electro-
lyte. Acetonitrile (Merck, Czech Republic) was used as organic
component in mobile phase for the purposes of HPLC analysis.
2.2. Apparatus
Electrochemical measurements were carried out using an AUTOLAB
PGSTAT-302N (Metrohm Autolab B.V., The Netherlands) potentiostat/
galvanostat controlled with NOVA 1.9 software. The three electrode sys-
tem consisted of Ag/AgCl/3 M KCl and platinum wire as reference and
counter electrode, respectively. BDDF electrode inserted in polyether
ether ketone (PEEK) body with inner diameter of disk of 3 mm, resistiv-
ity of 0.075 Ωcm and boron doping level of 1000 ppm (declared by
Windsor Scientific Ltd., United Kingdom as manufacturer) was used as
working electrode. The pH values of solutions were measured using
pH meter Model 215 (Denver Instrument, USA) with combined
electrode (glass-reference electrode), which was daily calibrated with
standard buffer solutions. All the potentials reported in this paper were
given against Ag/AgCl/3 M KCl reference electrode at a laboratory temper-
ature of 25 ± 1 °C.
2.3. Measurement procedures
A particular volume of standard solution of ADR was pipetted into a
25 mL volumetric flask, then filled up with the supporting electrolyte
and transferred quantitatively into voltammetric cell. Cyclic voltamme-
try (CV) and square-wave voltammetry (SWV) were employed without
deaeration since oxygen did not influence the oxidation of ADR. Five CV
voltammograms were obtained for each measurement, and the last scan
was always considered for the evaluation and making the figures re-
ported in this paper. SW voltammograms were recorded after optimiza-
tion of instrumental parameters (amplitude, frequency and step
potential). The peak currents (Ip) recorded using CV and SWV were
evaluated from the straight lines connecting the minima before and
after the peak maximum without background correction. Prior to the
first use, BDDF electrode was cleaned by rinsing with deionized water
and gently rubbed with a piece of damp silk cloth until a mirror-like ap-
pearance of surface was attained. Calibration curve was constructed
from the average of six replicate measurements for each calibration so-
lution of ADR and analyzed by linear least-square regression in
OriginPro 8.0 (OriginLab Corporation, USA) with the relevant results
(slope and intercept) reported with confidence interval for 95% proba-
bility. The detection limit was calculated as three times the standard de-
viation for the blank solution (supporting electrolyte) divided by the
slope of the calibration curve.
2.4. Preparation of human urine samples spiked with ADR
Human urine samples were collected from three healthy non-
smoking volunteers V1–V3 (co-authors) who did not undergo the treat-
ment by pharmaceuticals containing ADR. The determination of ADR in
human urine samples spiked with ADR was performed as follows: the
aliquot amount of standard solution of 1 mM ADR was added to the vol-
umetric flask containing 1 mL of fresh urine sample and subsequently
was diluted to 25 mL with supporting electrolyte (0.5 M HClO4). The
analysis was carried out by standard addition method in order to reduce
the matrix effect using the conditions described in previous sections.
3. Results and discussion
3.1. Electrochemical behavior of ADR on BDDF electrode
3.1.1. Effect of supporting electrolyte and pH
It is well-known that determination of electroactive compounds on
unmodified electrodes is sometimes difficult due to the absence of elec-
trocatalytic effect of appropriate modifier. The choice of the supporting
electrolyte is an important stage in electroanalytical studies because its
composition and pH influence the properties of analyzed solution as
well as the electrode–solution interface, modifying the thermodynam-
ics and kinetics of the charge transfer process. Cyclic voltammetry
(CV) was applied to examine the electrochemical behavior of ADR on
unmodified BDDF electrode. All necessary factors influencing the
current response of ADR were carefully checked to reach the conditions
at which the best analytical performance was achieved.
The electrochemical reaction mechanism of ADR and other catechol-
amines is familiar and has been elucidated in some papers [44–46]. ADR
usually undergoes a quasi-reversible two-electron oxidation in partici-
pation of two protons to form adrenalinquinone as evidenced in
Scheme 1. In our study, however, the reaction mechanism has not
been proved by any experimental data. In order to find the appropriate
medium for oxidation of 0.1 mM ADR the different supporting electro-
lytes such as nitric acid, sulfuric acid, hydrochloric acid, perchloric acid
and acetate buffer solution (ABS) were tested. Concerning ABS, two ox-
idation peaks at +0.70 V and +1.25 V were registered at pH 6 with two
small cathodic peaks at +1.15 and −1.20 V on the reverse scan on un-
modified BDDF electrode (Fig. 1). This phenomenon was observed in pH
values in the range 3–7 and well corresponded with literature data
 J. Sochr et al. / Diamond & Related Materials 43 (2014) 5–11 7

OH OH
HO NH O NH
CH3 CH3 + -
+ 2H + 2e

HO O
Adrenaline Adrenalinquinone

Scheme 1. Reaction of electrochemical oxidation of ADR.

when unprotonated form of adrenalinquinone is usually present above scan rate (inset of Fig. 2) within the studied range and the relations
pH 3 to allow for the cyclization reaction to form adrenochrome (the are expressed by Eqs. (1) and (2):
second oxidation peak) [45]. Moreover, it was found that with pH de-
crease of electrolyte, the oxidation peak at +0.70 V increased and the I ox ðADRÞ=μA ¼ ð0:640  0:125Þ=μA  
1=2 −1 2
peak at + 1.25 V decreased. In alkaline medium, the oxidation peaks þ ð1:553  0:027Þv =mV s R ¼ 0:999 ð1Þ
of ADR were distorted and the background current significantly grew
(results not presented). The use of moderate acid media (nitric acid, sul-
Ired ðADRÞ=μA
furic acid, hydrochloric acid) was inconvenient due to the bad-defined  
1=2 −1 2
oxidation peak of ADR with low and non-reproducible magnitude and ¼ ð1:721  0:217Þ=μA−ð1:083  0:019Þv =mV s R ¼ 0:997 :
relatively higher background current. Under strongly acidic conditions
ð2Þ
(pH b 1), the oxidation peak at +1.25 V completely disappeared in CV
voltammograms. Thus, in order to quantify ADR it was necessary to
choose the strongly acidic medium, in which only one peak These observations suggest that the diffusion is the rate-
appertaining to the oxidation of ADR to adrenalinequinone was ob- determining process in the electrode reaction of ADR and the rate-
served. It is evident from Fig. 1 that ADR underwent the single charge limiting adsorption and/or specific interactions on BDDF electrode sur-
transfer in perchloric acid (HClO4) on BDDF electrode providing a face are negligible. The slight shift of oxidation (reduction) peak
quasi-reversible wave with oxidation peak on the forward scan at potential towards more positive (negative) potential was observed as
about + 0.75 V and a smaller reduction peak on the reverse scan at the scan rate increased.
−0.10 V. As the optimal concentration of HClO4 with the highest oxida-
tion peak of ADR, 0.5 M HClO4 (pH 0.3) was selected from a variety of 3.2. Analytical performance
HClO4 tested solutions (0.1–2 M). It is also apparent that the back-
ground current was sufficiently low even at higher positive potentials 3.2.1. Effect of SWV instrumental parameters
on BDDF electrode which evidently proves the advantages and justness SWV is a pulse voltammetric technique proposing the benefits such
of the use of this electrode material. as speed (analysis time in a few seconds in comparison with about
2–3 min in differential pulse voltammetry) and desirable sensitivity as-
sociated with effective discrimination against the background current.
3.1.2. Effect of scan rate
This technique is applicable for trace determination of miscellaneous
The valuable information concerning the electrode reaction mecha-
electroactive organic compounds in various types of biological samples.
nism (rate-determining step) may be obtained from the relationship
The optimization of the SWV instrumental parameters affecting the cur-
between the peak current and scan rate (v). The effect of scan rate on
rent response of analyte is a useful step in the development of the elec-
the peak current of ADR (both oxidation and reduction peaks) was ex-
troanalytical methodology. Hence, the instrumental parameters such as
amined in the range of 5–500 mV s− 1 in 0.5 M HClO4 using CV on
amplitude, frequency and step potential were explored in order to find
BDDF electrode as shown in Fig. 2. The oxidation (Iox) and reduction
the optimum experimental set-up for electrochemical determination of
(Ired) peak of 0.1 mM ADR increased linearly with the square root of
ADR.

Fig. 2. Cyclic voltammograms of 0.1 mM ADR in 0.5 M HClO4 on BDDF electrode for series
of scan rates (v) of: (a) 5, (b) 10, (c) 25, (d) 50, (e) 75, (f) 100, (g) 150, (h) 175, (i) 200,
Fig. 1. Cyclic voltammograms of (a) 0 mM ADR in 0.5 M HClO4 and 0.1 mM ADR in (b) 0.5 (j) 250, (k) 300, (l) 400 and (m) 500 mV s−1. Both peak currents Ipa and Ipc as functions
M HClO4 and in (c) ABS at pH 6 on BDDF electrode with scan rate of 100 mV s−1. of scan rate v1/2 appear in the inset (error bars are constructed for six measurements).
8 J. Sochr et al. / Diamond & Related Materials 43 (2014) 5–11
Fig. 3. Square-wave voltammograms of 10 μM ADR in 0.5 M HClO4 on BDDF electrode
for various amplitudes: (a) 10, (b) 25, (c) 50, (d) 75, (e) 100, (f) 150, (g) 200, (h) 250
and (i) 300 mV at frequency of 50 Hz and step potential of 5 mV.
During optimization the amplitude was changed while the frequency
kept constant (50 Hz) and vice-versa (with fixed amplitude of 100 mV)
and only oxidation peak was studied for evaluation. It is evident from
Fig. 3 that the peak current of ADR increased as the amplitude was in-
creasing from 10 to 300 mV accompanied by the widening peak width
and clear shift of peak potential of ADR to the negative values. Addition-
ally, when the amplitude exceeded 150 mV, the peak current became
much wider (the distance minima before and after the peak maximum
represented more than 0.4 V). The variation of frequencies was studied
in the range of 10–100 Hz with peak current raising up to 100 Hz,
above which it became unsteady and the large current fluctuations
were observed (results not presented). By fixing the frequency of
50 Hz, the influence of step potential was also examined, because these
two parameters define the scan rate. At step potential greater than
5 mV, very few points were sampled, thus worsening the repeatability
of measurements. Overall, amplitude of 100 mV, frequency of 50 Hz
and step potential of 5 mV represent the optimum values with satisfac-
tory width and stability of current response of ADR and subsequently
were used for calibration curve construction.
3.2.2. Determination of ADR
Under the optimized experimental conditions, the applicability of
SWV for the determination of ADR was investigated by construction of
calibration curve by plotting the peak current against concentration of
Fig. 4. Square-wave voltammograms of different concentrations [ADR]: (a) 0, (b) 0.7, (c) 2,
(d) 4, (e) 6, (f) 10, (g) 30, (h) 40 and (i) 60 μM in 0.5 M HClO4 on BDDF electrode at opti-
mized SWV parameters: amplitude of 100 mV, frequency of 50 Hz and step potential of
5 mV. Peak current Ipa as a function of concentration [ADR] appears in the inset (error
bars are constructed for six measurements).
ADR in 0.5 M HClO4 on BDDF electrode (Fig. 4). This dependence
shows a good linearity (R2 = 0.998) in the concentration range from
0.7 to 60 μM as displayed in the inset of Fig. 4. The linear regression
equation may be expressed as Eq. (3):
Ip ðADRÞ=μA ¼ ð−0:012  0:002Þ=μA þ ð0:029  0:004Þ
 
2
 ½ADR=μM R ¼ 0:998 : ð3Þ
The low detection limit of 0.21 μM was obtained without any
chemical modification of BDDF electrode. The repeatability of the
proposed procedure was tested by fifty replicate SWV measurements
using 10 μM ADR under the same operating conditions over the short
time interval with relative standard deviation (RSD) of 3.5%. The low
RSD value revealed the excellent repeatability of method and confirmed
the low adsorption propensity of BDDF electrode surface to the oxida-
tion product of ADR. The method has appeared to be a suitable platform
for precise and sensitive quantification of ADR.
3.2.3. Interference study
In order to evaluate the selectivity of proposed method, the influence
of potential interfering agents (INT) commonly existing in the human
urine was investigated as follows: the addition of each one with
varying concentrations to solution with fixed concentration of 10
μM ADR (cADR/cINT = 1:1, 1:2, 1:5, 1:10, 1:20, 1:50 and 1:100) was accom-
plished under the same experimental conditions. In this context, the par-
ticular compound was considered to be serious interferent when it gave
the signal change value expressed as the ratio between the peak current
of ADR with (IADR + INT) and without (IADR) excess of interferent less
than 0.90. The results of influence of some urine biomolecules are given
in Fig. 5. It is apparent that the peak current of ADR was not significantly
affected by barbituric acid, folic acid and glucose in 100-fold excess as ev-
ident from the signal ratio value of more than 0.90. Concerning urea and
uric acid, the higher effect on the peak current of ADR was registered in
50-fold excess (signal ratio ~ 0.85–0.90). Ascorbic acid significantly influ-
enced the peak current of ADR already in 20-fold excess. Urea, uric and
ascorbic acid belong to the most known interfering compounds in analy-
sis of the human urine because of their close oxidation potentials on BDDF
electrode (0.3–0.8 V vs. Ag/AgCl electrode) often causing the overlapping
ot their peaks with oxidation peak of ADR. In spite of this fact we can con-
clude that the proposed method provided the sufficient selectivity for the
electrochemical determination of ADR.
3.2.4. Application of the method to the human urine samples spiked with
ADR
The standard addition method was applied for analysis of human
urine samples spiked with ADR when the aliquot amount of standard
solution of ADR was added for evaluation of the accuracy and the prac-
tical usefulness of proposed electrochemical method. The preparation of
these samples is described in Section 2.4. The average results of six rep-
licate measurements expressed as confidence interval for 95% probabil-
ity determined in human urine samples spiked with ADR using the
proposed method are summarized in Table 1. The recovery values be-
tween 98 and 102% indicated that there are no significant interferences
of matrix of the human urine as well as that the method is sufficiently
accurate and suitable for quantification of ADR. Fig. 6 shows an illustrat-
ed example of analysis of urine sample of first volunteer in the absence
and after addition of some aliquot amounts of ADR standard.
3.2.5. Comparison with other electrochemical methods
The comparison between the analytical performance of the pro-
posed method and some published papers dealing with determination
of ADR from last years is given in Table 2. As it was mentioned, no official
attempt for electrochemical determination of ADR on BDDF electrode
has been published until now in the literature. Generally, it is clear
from Table 2 that the electrochemical methods using carbon nanotubes
 J. Sochr et al. / Diamond & Related Materials 43 (2014) 5–11 9

Fig. 5. The influence of some interfering compounds (INT) on the current response of ADR expressed as the ratio between the peak current of ADR with (IADR + INT) and without (IADR)
excess of interferent in various concentration ratios ([ADR]/[INT]) in 0.5 M HClO4 on BDDF electrode. The experimental conditions were the same as those in previous measurements.

as modifiers for glassy carbon (GCE) or carbon paste (CPE) electrode are
considered to be the most sensitive for the determination of ADR with
the lowest detection limits on the concentration level of 10− 8 M
[19–23]. The polymer-modified or platinum and gold modified
electrodes have been applicable for electrochemical determination
of ADR with detection limits in the range of 10−7–10−8 M
[25,27–32,34]. Thus, the sensitivity of chemically modified electrodes in
the determination of ADR is indubitable; however, their preparation
often prolongs the overall time of procedure because of the complicated
surface modification. This process requires the incorporation of the mod-
ifier to the electrode surface which sometimes leads to the low reproduc-
ible results. Moreover, the stable electrochemical signal usually involves
the certain time to reach the equilibration between analyte and modified
electrode and the results allow the variableness of analytical parameters
(slope and intercept) due to the differences in the actual state of electrode
surface. Therefore, it is sometimes redundant to modify the electrode sur-
face for selectivity and sensitivity improvement in routine analytical prac-
tice. This fact may appear to be less relevant; however this occurrence
decreases the number of operations in analytical procedure (lower risk
of measurement errors) and reduces expenses and operational skills of
analyst. The advantage of using the unmodified BDDF electrode in this
specific practical application consists in comparable detection limit of
ADR with those reported for the modified electrodes. This may still be
good enough for many cases in the clinical applications.
The other electrochemical approach for the determination of ADR
using carbon fiber ultramicroelectrode (CFUME) consists in a combina-
tion of preconcentration step (adsorption of ADR) with electrochemical
activation of electrode surface necessary to provide a constant current
response of ADR prior to use [36]. Otherwise, this effect reduces the de-
tection limit of ADR (0.04 μM) but also prolongs the whole determina-
tion process in regard to the demand of activation of electrode surface.
On the other hand, presented procedure is based explicitly on
diffusion-limiting process (with negligible impact of adsorption) with-
out any electrochemical pretreatment of BDDF electrode surface
although with five-times higher detection limit when compared with
CFUME. Concerning the bare GCE [37], the suggested procedure is
rapid, simple and suitable mainly for determination of ADR in pharma-
ceutical formulations because of lower sensitivity despite of using
differential pulse mode. To summarize, BDDF electrode without any
chemical and electrochemical pretreatments of its surface with SWV
technique fulfills the demands of modern electroanalytical chemistry
(rapidity, simplicity, sensitivity, repeatability and low cost).
4. Conclusions
According to our knowledge, BDDF electrode was employed for the
first time in combination with SWV to elaborate the novel, simple,
rapid and cheap alternative analytical method for quantification of
ADR. The low detection limit of 0.21 μM was achieved without using
any chemical and electrochemical pretreatment of electrode surface.
In addition, it is comparable with those reported in previous papers
dealing with chemically modified electrodes. The proposed procedure
was applied for analysis of human urine spiked with ADR with good re-
coveries (98–102%). By this study we would like to demonstrate that
BDDF electrode may be used as sensitive drug sensor in clinical analysis
of various biologically active compounds and may replace complex and
expensive chromatographic methods. However, the proposed method
can be limited in monitoring of ADR in clinical analysis in the presence
of high excess of other drugs in urine, especially ascorbic acid.

Table 1
Determination of ADR in human urine of three volunteers (V1–V3) spiked with ADR using
proposed method (n = 6).

Sample Added Founda Recoveryb

(μM) (μM) (%)

V1 6.19 (6.29 ± 0.14) 102

V2 5.54 (5.60 ± 0.09) 102
V3 7.86 (7.73 ± 0.17) 98
Fig. 6. Square-wave voltammograms of analysis of urine sample of volunteer (V1) after
a
Confidence interval calculated according [x ± tn − 1,α SD / n1/2]; t5; 0.05 = 2.0150. addition of ADR to reach the concentration [ADR]: (a) 0, (b) 6.19, (c) 9.21, (d) 16.3, (e)
b
Calculated as found concentration values divided by added ADR concentration values 28.1 and (f) 31.5 μM ADR in 0.5 M HClO4 on BDDF electrode. The experimental conditions
multiply by hundred. were the same as those in previous measurements.
10 J. Sochr et al. / Diamond & Related Materials 43 (2014) 5–11

Table 2
Comparison of the proposed method with some previously reported electrochemical methods for determination of ADR.

Working electrode Modifier Supporting electrolyte Technique Linear concentration range Detection limit Application Ref.
(μM) (μM)

GCE HT/MWCNT PBS, pH 7 DPV 0.078–0.2 0.02 Urine [19]

CPE FePC/MWCNT PBS, pH 7.4 DPV – 0.21 Blood serum [20]
CPE IL/CNT PBS, pH 7 DPV 0.3–450 0.09 Urine, serum, drugs [21]
GCE SWCNT/CHIT/IL PBS, pH 7 DPV 1–580 0.09 Urine, blood [22]
GCE PP/MWCNT PBS, pH 6 DPV 0.1–8 0.04 Serum [23]
AuE PMP PBS, pH 7.2 DPV – 0.1 – [25]
GCE Au/PP PBS, pH 7 DPV 0.3–21 0.03 Urine [27]
PIGE PR PBS, pH 7 DPV 3–90 0.8 – [28]
GCE PT PBS, pH 7.4 DPV 2–600 0.3 – [29]
GCE PMP PBS, pH 4 SWV 0.75–200 0.17 Drugs [30]
CPE PtNP/IL/LAC PBS, pH 6.5 SWV 0.99–210 0.29 Drugs [31]
GCE Pt-AuNP PBS, pH 7 DPV 63–400 57 Drugs [32]
AuE AuNP/DTT PBS, pH 7 CV 0.1–8 0.06 Drugs [34]
CFUME – PBS, pH 8 CV 10–100 0.04 Urine [36]
GCE – 1 M H2SO4 DPP 10–100,000 – Drugs [37]
BDDFE – 0.5 M HClO4 SWV 0.7–60 0.21 Urine This work

Abbreviations: AuNP: gold nanoparticle, BDDFE: boron-doped diamond film electrode, CHIT: chitosan, CFUME: carbon fiber ultramicroelectrode, CPE: carbon paste electrode, CV: cyclic
voltammetry, DPP: differential pulse polarography, DPV: differential pulse voltammetry, DTT: dithiothreitol, GCE: glassy carbon electrode, HT: hematoxylin, IL: ionic liquid, LAC: laccase,
MWCNT: multi-walled carbon nanotube, PBS: phosphate buffer solution, PC: phthalocyanine, PIGE: paraffin-impregnated graphite electrode, PMP: polymethoxyphenol, PP: polypyrrole,
PR: polyrutin, PT: polytaurine, PtNP: platinum nanoparticle, SWCNT: single-walled carbon nanotube, SWV: square-wave voltammetry.

Prime novelty statement
By our manuscript we would like to inform the scientific community
in analytical chemistry about powerful features of (unmodified) boron-
doped film diamond electrode as sensitive drug sensor for the detection
and quantification of adrenaline. It is important to point out that there is
no published report dealing with electrochemical determination of
adrenaline on boron-doped diamond film electrode yet to date in acces-
sible literature.
Acknowledgments
This work was supported by the Grant Agency of the Slovak Republic
(grant No. 1/0051/13) and the Slovak Research and Development
Agency under the contract No. APVV-0797-11.
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