Journal of

Electroanalytical
Chemistry
Journal of Electroanalytical Chemistry 609 (2007) 1726
www.elsevier.com/locate/jelechem

On the electrochemistry of dopamine in aqueous solution. Part I:

The role of [SDS] on the voltammetric behavior of dopamine
on a carbon paste electrode
Silvia Corona-Avendano a, Georgina Alarcon-Angeles b, Mara Teresa Ramrez-Silva b,
Giselle Rosquete-Pina a, Mario Romero-Romo a, Manuel Palomar-Pardave a,*
a
Universidad Autonoma Metropolitana-Azcapotzalco, Departamento de Materiales, Av. San Pablo #180, Col. Reynosa-Tamaulipas,
C.P. 02200, Mexico, D.F., Mexico
b
Universidad Autonoma Metropolitana-Iztapalapa, Departamento de Qumica, Av. San Rafael Atlixco #186, Col. Vicentina,
C.P. 09340, Mexico, D.F., Mexico

Received 13 April 2007; received in revised form 19 May 2007; accepted 29 May 2007
Available online 13 June 2007

Abstract

From CV and HPLC experiments, the inuence of [SDS] on the dopamine electrochemical behavior was determined in aqueous solu-
tion. It is shown that in the absence of SDS the dopamine electrochemical oxidation at a carbon paste electrode is a quasi-reversible
process, mass transfer controlled that is coupled to a slow chemical reaction (EC mechanism), however, as the [SDS] in solution is
increased, the heterogeneous standard rate constant, k0, drastically increases. When [SDS] reaches a value of 5 mM, which is higher than
the corresponding critical micellar concentration (CMC), the dopamine electrooxidation reaction becomes adsorption controlled and the
chemical reaction is avoided. In all these cases, it was found that, the electrode reaction involves a monoelectronic transfer step. From
HPLC experiments it was found that, after imposing a macroelectrolysis (oxidation) of dopamine, two products were detected except
when the [SDS] in solution was 5 mM. In this case, just one product was formed corresponding to that having the highest retention time,
which can be associated to dopamine semiquinone.
 2007 Elsevier B.V. All rights reserved.

Keywords: Dopamine; SDS; Heterogeneous standard rate constant

1. Introduction niques coupled with electrochemical detectors [35]. How-

Dopamine, DA, is a neurotransmitter known to play a
very important role in the central nervous system, which
when present in low concentrations is likely to give rise
to neurodegenerative diseases such as Parkinson and Alz-
heimer [1,2], among others. Therefore, it is quite an essen-
tial task to eect its precise determination in extracellular
uids, even though this has been undertaken mostly by
analytical facilities usually using chromatography tech-
*
Corresponding author. Tel.: +52 5553189472; fax +52 5553189087.
E-mail address: mepp@correo.azc.uam.mx (M. Palomar-Pardave).
ever, up to now it has been common occurrence that the
majority of samples thus subjected to analyses contain
ascorbic acid, AA, in such concentrations that these pose
interference problems to be contended with, because of
the overlap of their individual electrochemical signals, aris-
ing from the fact that their oxidation potentials are indeed
quite close.
The said situation has led to perform diverse studies to
determine the DA in the presence of AA by means of vol-
tammetry techniques such as cyclic voltammetry, CV, and
dierential pulse voltammetry, DPV, also using specially
modied electrodes specic to selected electroactive species,
such as the cationic surfactants cetylpyridinium chloride,

0022-0728/$ - see front matter  2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jelechem.2007.05.021
18 S. Corona-Avendano et al. / Journal of Electroanalytical Chemistry 609 (2007) 1726
cetyltrimethylammonium bromide, amongst others [621].
Wen et al. [7] have studied the advantages of performing
this determination using the micellar properties of some
surfactants, such as sodium dodecyl sulphate, SDS, on a
glassy carbon electrode. This happens to be so due to the
surfactants adsorption on the electrode and solubilization
of electroactive compounds on micellar aggregates, which
may duly induce changes in the redox potential, the energy
transfer coecients and the diusion coecients of the spe-
cies located within the electrodes vicinity, as was reported
by Wen et al. [7] for ascorbic acid and its lipophilic deriv-
atives in the presence of CTAB and SDS micelles. Also,
SDS has been used for the determination of some biologi-
cal compounds like epinephrine, uric acid, guanine and
acetaminophen [22]. Recently, Zheng and Zhou [23] have
proposed the use of SDS-modied carbon paste electrodes,
formed by pre-adsorbing the SDS to determine selectively
dopamine in the presence of ascorbic acid. Considering
the aforementioned, in the rst part of the present work,
we analyze the inuence of SDS concentration on the elec-
trochemical behavior of dopamine oxidation when both,
SDS and DA are present in the same solution, and in the
second we will show the eectivity of this approach to
undertake the selective determination of DA in the pres-
ence of AA.
2. Experimental
2.1. Reagents and chemicals
All solutions were made from Mercks analytical grade
reagents and deionized water type 1 with 18.2 MX resistiv-
ity, free from organic matter, obtained from a US Filter
PURE-LAB Plus UV. The pH was adjusted to pH 2.10
with HCl also from Merck. The resulting solutions were
deaerated with nitrogen and freshly prepared prior to each
determination. They were also protected from the incidence
of light even during the performance of the experiments.
2.2. Instrumentation
The electrochemical determinations were carried out
with the aid of a BAS 100 W 2.5 potentiostatgalvanostat
coupled to a PC running the BAS 100 W 2.5 software to
allow experimental control and data acquisition. A typical
three electrode cell was used where a carbon paste elec-
trode, CPE, was the working electrode. The CPE was pre-
pared as usual, by mixing the Johnson Matthey 1 lm,
99.9% graphite powder with nujol as indicated elsewhere,
Ramrez-Silva et al. [24,25]. A platinum wire (BAS MW-
1032) was the counter electrode, while saturated Ag/AgCl
(BAS MF-2052) was the reference electrode, against which
all potentials (E) reported in this work were measured.
Macroelectrolysis experiments were performed with a Pt
mesh as working electrode.
The pH readings within the 014 pH range were done
with a TACUSSEL potentiometer LPH 430T pH-METER
coupled to a CORNING combined glass electrode. High-
performance liquid chromatography was carried out
through a Spectra System SCM 1000 Thermo Separation
Products provided with a spectrophotometry detector
made by an array of diodes and a Grom-sil 120, ODS-
5ST 5 lm, 250 mm column, with 4 mm ID. The mobile
phase was a phosphate buer at pH 3.0. Also, an ampero-
metric detector was used having identical electrodes to
those used in the BAS instrument.
2.3. Procedure
The electrochemical behavior of DA was studied by cyc-
lic voltammetry, CV, in the system CPE/0.01 M NaCl, x M
SDS where x 2 {0, 0.075, 0.5, 5 mM}, maintaining a nitro-
gen atmosphere and controlled temperature (25 C) in the
cell. The CVs were recorded in the 600 mV to 1000 mV
interval applying dierent potential scan rates, namely,
10, 1000 mV s1. In all cases, the potential sweeps started
at the open circuit or nil current potential (Ei=0).
The macroelectrolysis experiments were done by apply-
ing dierent oxidation potentials, depending on the SDS
concentration, to achieve the same current density for each
solution during 5 min. After this electrolysis, 20 lL of the
solution were injected to the chromatograph tted with
spectrophotometric and amperometric detectors that were
used imposing a constant wavelength (k = 480 nm) where
DA absorption is negligible, and a constant potential
(E = 315 mV), which correspond to a DA reduction zone,
respectively.
The interfacial tension c was evaluated from the experi-
mental electrocapillary plots of drop time vs. potential
using the BAS CGM cell by means of the dropping mer-
cury electrode (DME) Mode and a 150 mm inner diameter
(i.d.) capillary with a mass ow of 4.36 106 kg s1 and a
drop time of about 3 s.
25 Epa
20
15
10
5
i / A
0
-5
-10
Epc
-15
-20
-25
-500 -200 100 400 700 1000
E / mV
Fig. 1. Experimental cyclic voltammograms recorded in the system CPE/
0.1 M NaCl, 0.01 M HCl (pH 2.10) for two dierent DA concentrations: 0
() and 2.5 104 M (- - - - - -). In both cases the potential sweep started
at the corresponding open circuit potential in the positive direction at
100 mV s1 scan rate.
 S. Corona-Avendano et al. / Journal of Electroanalytical Chemistry 609 (2007) 1726 19

3. Results and discussion H H H

H
H +H O HH
O N H
3.1. DA electrochemical oxidationreduction process H
H H
in the absence of SDS H
+
H

H O N
O
HH
Fig. 1 shows a typical voltammetry behavior of the DA H H
H
2.5 104 M in the system CPE/HCl 0.01 M (pH 2.10)
R4
(Ei=0 = 304 mV), in the positive direction, broken line;
when there is no DA in the system, solid line, there was H
H HH
no peak within this potential interval. In the presence of H H H N H
H +
DA an oxidation peak was observed, Epa, at 589 mV O NH O
H HH
potential, which could correspond to one or more electro- H
H + H+
chemical reactions shown in the following reaction path H
O H O
(R1)(R3): H
H

R5

H O H O
H
H
H H
O H H H
N H
+ O H +
R1
H N H +
H
H
H H
H
+ 1e- + H
H
H H H H

H O H H H
H H +
O NH
H H
O H H H +
+
N H H + 1e- + H R2
H
H H O H
H H
H

H O
H H H H
H +
H O NH
O H H H
+
N H + R3
H H
H
H
H
H + 2e- + 2H
H H O H

Most of the studies regarding the DAs electrochemical
oxidation have associated this process with reaction (R3)
[15,23,3036] to form dopamine quinone. However, there
are some studies which claim that DA oxidation occurs
through monoelectronic steps (as in (R1) and (R2)) consid-
ering then that the semiquinone form of DA may be stabi-
lized [7,35,37,38]. The latter studies involve the DA
electrochemical oxidation using a polymer lm-modied
electrode [35], self-assembled monolayers [37] or micellar
aggregates [7]. It is important to mention that some authors
have proposed an EC mechanism for the electrochemical
DA oxidation where the electrochemical reaction (E) is
given by (R3) and the chemical reaction (C) corresponds
to one of the following reactions, (R4), to form leucodop-
achrome by intramolecular cyclization or (R5) to form
aminochrome by dopamine quinone deprotonation [7]:
Zhang and Dryhurst [36] investigated the electrochem-
ical oxidation of DA at physiological pH in aqueous
solution on a pyrolytic graphite electrode and proposed
an ECC mechanism corresponding with the sequence
(R3), (R5) and (R6) where (R3) is a reversible reaction.
It is important to stress out that Young and Babbitt
[39] studied the DA anodic melanization reactions at
the CPE in 1 M HCIO4 and in McIlvaine buers of
varying pH (from 6.1 to 7.2) at 15, 20, 25, and 30 C.
They found that the DA underwent an ECC mechanistic
sequence involving an initial two-electron oxidation to a
quinone (R3), which after deprotonation to the amine
group (R5) cyclized rapidly to the 5,6-dihydroxyindolines
(R6), however, in this case the E reaction was not a
reversible one, with a potential peak dierence (DE =
Epa  Epc) ca. 280 mV.
20 S. Corona-Avendano et al. / Journal of Electroanalytical Chemistry 609 (2007) 1726

H HH
H
H Fig. 2 depicts a family of CV recorded in the system
N H
O
O H
HH
H inuence of the potential scan rate on the voltammetric
O O
H H
H
Another mechanism associated with DA electrochemical
oxidation involves an ECE pathway where the rst E reac-
tion corresponds again to (R3), the chemical with (R4) and
the second electrochemical reaction to (R7) [31].
H CPE/0.01 M HCl (pH 2.1), 2.5 104 M DA at dierent
potential scan rates. From this gure it was possible to
H gather the information shown in Table 1 regarding the
N
H
parameters of this system.
From the variation of DE values with the potential scan
R6 rate, shown in Table 1, one may conclude in this case, that
the DA electrochemical oxidation is a quasi-reversible
mass transfer-controlled process, see Fig. 3. However,
the behavior of the ratio jipc/ipaj may indicate the presence
of a coupled chemical reaction. If this is so, a plausible

H H
O HH O
HH
H +
2e- + 2H R7
HH HH
+ +
O N O N
HH HH
H H H

Recently, Li et al. [40] have proposed a more complex
(ECECEE) mechanism for DAs oxidation in aqueous
solution (pH > 3.86) which includes further isomerization
(R8) and oxidation of the cyclization product (R9) lead-
ing to polymer growth (poly(5,6-indolequinone)). It
becomes plain for all previous reactions that the pH
can certainly play a very important role to establish the
most probable DA oxidation mechanism. Recently, our
group has shown by an experimental and theoretical
approach, which is the most probable DA deprotonation
pathway [41].
H
H H
HH O
O H
H H
H D
O N
O N
H H H H
H RT
R8
possibility for this chemical reaction is directly related
with reaction (R10). Moreover, in accordance with Gosser
[42], who describes a simplied two-dimensional zone
diagram for the EC mechanism, see Figs. 215 in Ref.
[42], our case would correspond to an EC mechanism
where both, the electrodic and chemical kinetics are
slow.
In order to support further the conclusion regarding the
electrochemical reaction, the variation of the potential
peaks as a function of the scan rate was analyzed, see
Fig. 4. Both the anodic and cathodic peak potentials
depend linearly on the logarithm of the scan rate as
predicted by Eqs. (1) and (3) proposed by Aoki et al.
[43]
  1=2  
Epa E0 m 0:78 ln  0:5 ln m 0:5m ln v 1
k0
m 2
1  anF 

H H
H H
O O
H
+
H H 2e - + 2H R9
+
H
+
O N O N
H HH
H H H


 1=2  
During the inverse potential sweep one reduction peak 0 D
(Epc) at 171 mV was formed. The DE was 418 mV. This
0
Epc E  m 0:78 ln  0:5 ln m  0:5m0 ln v
0
k0
value was much higher than that expected, 58 mV for 3
n = one electron or 60 mV/n for multielectron transfer, 0 RT
m 4
for a reversible system [2629,42]. anF 
 S. Corona-Avendano et al. / Journal of Electroanalytical Chemistry 609 (2007) 1726 21

80 0.70

1000 0.60
60
900
0.50
40 500
350
0.40

Ep / V
300
i / A

20 150
0.30
50
10
0 0.20

0.10
-20
0.00
-40 0.00 2.00 4.00 6.00 8.00
-500 -300 -100 100 300 500 700 900 ln (v )
E / mV
Fig. 4. Relationship between the peak potential Ep, anodic (s) and
Fig. 2. Family of experimental cyclic voltammograms recorded in the cathodic (d), and the scan rate ln v, obtained from CVs in Fig. 2. Lines are
system CPE/0.1 M NaCl, 0.01 M HCl (pH 2.10), 2.5 104 M DA at the result of the linear tting procedure.
dierent potential scan rates.

k0 was calculated as 0.0029 and 0.0038 cm s1, for

Table 1 the anodic and the cathodic branches, respectively; the
Variation of the voltammetric parameters as a function of the potential
scan rate (v) corresponding to the CVs shown in Fig. 2
average value is 0.0034 cm s1. Interestingly, if we use
D = 5.40 106 cm2 s1 in Eqs. (1) and (3) instead of
v/ Epa/ Epc/ (Epa  Epc)/ ipa/ ipc/ jipc/
mV s1 mV mV mV lA lA ipaj
4.15 106 cm2 s1 the average value of k0 changes to
0.0039 cm s1 which is a very small dierence. This value
1000 629 121 508 65.44 33.73 0.52
500 609 131 478 44.96 21.32 0.47
indicates that at the scan rate range considered, the DA
350 599 141 468 38.83 19.58 0.50 oxidationreduction process is a quasi-reversible one. It is
150 569 151 448 24.50 11.78 0.48 important to mention that, in [37] the DA diusion coe-
50 579 181 388 15.04 7.114 0.47 cient was measured in an aqueous solution containing as
10 539 241 298 6.87 2.823 0.41 supporting electrolyte a phosphate buer (pH 6.81) at
20 C. Even when the experimental conditions are not ex-
actly the same, it is expected that the D value for dopamine
where E0 is the formal potential of DA ((Epa + Epc)/ in aqueous solution does not change drastically, for in-
2) = 0.39 V, D is the diusion coecient, k0 is the heteroge- stance Young and Babbitt [39] found a diusion coecient,
neous standard rate constant, a is the energy transfer coef- derived from chronoamperometry, for DA of 5.40
cient and n is the number of electrons transferred during 106 cm2 s1 for a 1 M HClO4 aqueous solution at 25 C.
the heterogeneous reaction. R, T and F are the universal Therefore, from the experimental variation of the anodic
gas constant, absolute temperature and Faraday constant, peak current (ipa) as a function of E  E0, see Fig. 5, and
respectively. From the slope and intercept of the straight Eq. (5) [29], it is possible to estimate the value of the energy
lines in Fig. 4 and using the reported value of DAs transfer coecient, a, which in our case was 0.47. Using
diusion coecient, 4.15 106 cm2 s1 [37], the value of this a value, Eqs. (2) and (4) and the slope of lines in

80 80

60 60
i pa / A
i pa / A

40 40

20 20

0 0
0 10 20 30 40 0 100 400 600 800 1000
-1
v 1/2 / mV1/2s-1/2 v / mVs

Fig. 3. Variation of the anodic peak currents, ipa, as a function (a) v1/2 and (b) v recorded in the system CPE/0.1 M NaCl, 0.01 M HCl (pH 2.10),
2.5 104 M DA. The open circles correspond to the experimental data, while the line in (a) is the result of the linear tting procedure.
22 S. Corona-Avendano et al. / Journal of Electroanalytical Chemistry 609 (2007) 1726

-9 -10

-9.5 -10.5

-10
-11
-10.5

lni pc
lnipa

-11.5
-11
-12
-11. 5
-12.5
-12

-12.5 -13
0.10 0.15 0.20 0.25 0.30 -0.30 -0.25 -0.20 -0.15 -0.10
0 0
E pa- E / mV Epc- E / mV
0
Fig. 5. Experimental variation of the peak current as a function of the dierence Ep  E (points) for both the anodic (a) and cathodic (b) processes. The
line corresponds to the linear t of the experimental data (a) ln ipa= 18.12(Epa  E0)  14.66 and (b) ln ipc = 18.97 (Epc  E0)  15.6.

Fig. 4, one can estimate the number of electrons involved
during DA oxidation and reduction process, as 0.93 and
0.95, respectively. From this result it is possible to conclude
that DA oxidation occurs in this case through monoelec-
tronic steps as indicated in (R1)
ip 0:227FAC 0 k 0 expaf Ep  E0 
where A is the electrode surface area, C 0 is the DA concen-
tration and f = F/RT
From this gure it is possible to note that practically, the
SDS does not show electroactivity, especially for the
[SDS] < CMC, where the DA does. However, for the high-
est [SDS] value considered, which is higher than the CMC,
some activity can be noted, particularly in the anodic zone.
In order to verify if the SDS may produce any interfer-
5
ence with the DA, particularly at concentrations higher
than the CMC, Fig. 8 shows a comparison between two
CV recorded in the system CPE/0.1 M NaCl, 0.01 M HCl

H O H
H O HH
H
H
O H H
+ H + H
+ R10
N H H
H +
H H O N
H HH
H H H

3.2. DA electrochemical oxidationreduction process (pH 2.10), 5 mM SDS with and without DA. From this g-
in the presence of SDS ure it is possible to note that there is no interference from
the SDS on the anodic and cathodic response of the DA,
Given the amphiphilic nature of the SDS molecules, it however, it is clearly noted that DE diminish and both
may form in aqueous solutions aggregates named micelles. the anodic and cathodic peak currents increase.
The critical micellar concentration (CMC) determines the
concentration (C) value in which the surfactant molecules 0.45
present in solution tend to form micelles (C > CMC) or
where they are mainly present as a monomer (C < CMC)
0.43
[44]. Therefore, it is an important experimental value to
be determined at the conditions used. A method to deter-
-1
/ Nm

mine CMC consists in measuring the variation of the inter- 0.41

facial tension (c) as a function of the [SDS] (see Fig. 6).
From this gure it was possible to establish the critical 0.39
micellar concentration that for this system corresponds to CMC = 1.38 mM
1.38 mM.
0.37
-6 -5 -4 -3 -2 -1
3.2.1. SDS electroactivity log [SDS] / M
Fig. 7 depicts the electrochemical behavior of the system Fig. 6. Variation of the experimental interfacial tension (s) with the
CPE/0.1 M NaCl, 0.01 M HCl (pH 2.10) with dierent logarithm of the surfactant concentration, recorded in the system Hg/
[SDS] in the range around the experimental CMC found. 0.1 M NaCl(aq), x M SDS(aq).
 S. Corona-Avendano et al. / Journal of Electroanalytical Chemistry 609 (2007) 1726 23

50
35 5

30 0.5
25 0.07
c
0
10
15

i / A
i / A

5 -10
b

-5 a -30

-15 -50
-500 -200 100 400 700 1000 -500 -200 100 400 700 1000
E / mV E / mV

Fig. 7. Experimental cyclic voltammograms recorded in the system CPE/ Fig. 9. Experimental cyclic voltammograms recorded in the system CPE/
0.1 M NaCl, 0.01 M HCl (pH 2.10) with dierent SDS concentrations: (a) 0.1 M NaCl, 0.01 M HCl (pH 2.10), 2.5 104 M DA with dierent SDS
0.075, (b) 0.5 and (c) 5 mM at 100 mV s1 potential scan rate. concentrations indicated in the gure, in mM. In all cases the potential
scan rate was 40 mV s1.

50
E pa Table 2
Variation of the voltammetric parameters, gathered from the plots shown
30 in Fig. 9, as a function of the [SDS]
[SDS]/ Epc/ Epa/ DE/ ipa/ ipc/ ipc/ 102k0/
10 mM mV mV mV lA lA ipa cm s1
i /A

0 171 579 408 14.9 7.09 0.48 0.3a

-10 0.075 371 509 138 20.48 10.89 0.53 2.8a
0.5 415 475 60 27.06 17.72 0.65 8.6a
-30 5 431 469 38 38.95 40.75 1.00 82b
The heterogeneous rate constant (k0) estimated at each SDS concentration
E pc
-50 is also reported.
a
-500 0 500 1000 These values were estimated from the experimental variation of Ep vs.
E / mV ln v, recorded at the respective [SDS], and using Eqs. (1) and (2).
b
Estimated from Eq. (7) and the experimental DEp value, see Table 3,
Fig. 8. Cyclic voltammograms recorded in the system CPE/0.1 M NaCl, recorded at 40 mV s1.
0.01 M HCl (pH 2.1), 5 mM SDS for two dierent DA concentrations: 0
() and 2.5 104 M ( ). In both cases the potential scan rate was
40 mV s1.
100 100
100
80
80
80
3.2.2. Eect of [SDS] on the voltammetric behavior of DA 60
i pa / A

60 70
40 50
Fig. 9 shows a set of CVs recorded in the system CPE/ 40 20 40
0.1 M NaCl, 0.01 M HCl (pH 2.10), 2.5 104 M DA with 20 0
0 20 40 60 80 100 120 20
30
i / A

dierent [SDS]. Table 2 summarizes the voltammetric 0

v / mVs
-1
10
parameters gathered from the plots shown in Fig. 9. Note -20
that as the [SDS] increases in the system, DE drastically -40
diminishes while the ratio ipc/ipa tends to unit. When
-60
the [SDS] < CMC (00.5 mM) the DA electrochemical oxi-
-80
dation changes from a quasi-reversible system to a revers-
-100
ible one, however, when the [SDS] > CMC (5 mM) the -800 -600 -400 -200 0 200 400 600
system presents features corresponding to an adsorption- 0
E - E / mV
controlled process. In order to corroborate this possibility,
Fig. 10. Experimental cyclic voltammograms recorded in the system CPE/
experimental CVs were recorded in this system applying
0.1 M NaCl, 0.01 M HCl (pH 2.10), 2.5 104 M DA, 5 mM SDS
dierent potential scan rates, see Fig. 10. From these, recorded at dierent potential scan rates shown in the gure in mV s1.
the full peak width at half-height (EFWHH) and DE, see Inset shows the variation of ipa as a function of v, (d) corresponds to the
Table 3, and ipa (see inset in Fig. 10) were obtained as a experimental data, while the line is the result of the linear tting
function of the potential scan rate. In all cases the variation procedure.
of these parameters as a function of v is the expected one
when strong adsorption of the electroactive species is tak- Murray et al. [45,46] developed a theory for electrode
ing place [29,42]. kinetics of surface-immobilized monolayers in cyclic
24 S. Corona-Avendano et al. / Journal of Electroanalytical Chemistry 609 (2007) 1726

Table 3 Considering the above features observed on the CVs

Variation of the voltammetric parameters, gathered from the plots shown recorded at [SDS] = 5 mM, see Fig. 10, and considering
in Fig. 10, as a function of the potential scan rate
the case where the adsorbed species is electroactive
v/mV s1 DEp/mV EFWHM/mV n k0/s1 [29,42,47] Eq. (9) has been proposed to describe the exper-
10 18 120 0.8 0.26 imental iE curves
20 28 100 0.9 0.46 h  i
30 28 80 1.1 0.69  00
40 38 80 1.1 0.82 n2 F 2 vACO bO =bR exp nF =RT E  E
i n h  io2 9
50 48 90 1.0 0.92 RT 0
70 48 90 1.0 1.28 1 bO =bR exp nF =RT E  E0
80 48 90 1.0 1.47
100 68 100 0.9 1.46 where the reduction potentials refer to the unabsorbed spe-
The heterogeneous rate constant (k0) and the number of electrons trans- cies and CO is the surface coverage, bO an bR are related to
ferred (n), estimated using Eqs. (7) and (8), respectively, are also reported. the adsorption free energy DG0ads through Eqs. (10) and
(11), respectively
voltammetry based on the Marcus free energy-rate rela- bO expDG0ads;O 10
tion. In the framework of this theory, the estimation of
bR expDG0ads;R 11
the standard rate constant, k0, can be made from DEp
experimental data without exact knowledge of the reorga- The peaks potential and current are:
nization energies. This analysis follows a Marcus-DOS    
model that takes into account the continuum of electronic 0 RT bO
Ep E0  ln 12
states in the metal electrode by integration of the Marcus nF bR
equation over those states as shown below: n2 F 2
  2   ip vACO 13
kg kB T 4RT
Z 1 exp  x  kB T 4k
k g lqk B T dx 6 Substituting Eqs. (12) and (13) in (9) yields the following
1 1 expx equation:
where kg is the rate constant at the electrode over-potential 0
4ip bO =bR expnF =RT E  E0 
g, k is the reorganization barrier energy, and the pre-expo- i 0 2
14
nential factor includes the distance-dependent electronic f1 bO =bR expnF =RT E  E0 g
coupling parameter, l, and the density of electronic states A parameterized form of Eq. (14) is the following equation:
in the metal electrode, q. Cyclic voltammograms were dig-
P 1 P 2 expP 3 E  P 4 
itally simulated based on Eq. (6) assuming a k = 0.85 value i 2
15
for water to develop working curves (at 298 K) of DEp vs. f1 P 2 expP 3 E  P 4 g
log(v/k0) where v is the potential sweep rate and k0 is the where
standard electron-transfer rate at the zero over-potential.
These working curves, which are relatively insensitive to P 1 4ip 16
the assumed value for k, see Table 1 in [45], were used to bO
extract values of k0 from experimental DEp values. Eq. P2 17
bR
(7) is a valid approximation of such working curves for nF
DEp > 10 mV P3 18
RT
  0
v P 4 E0 19
DEp 201:39 log 0  301:78 7
k
Fig. 11 depicts a comparison of some experimental CVs
From the experimental DEp values, see Table 3, and Eq. (7) recorded in the system CPE/0.1 M NaCl, 0.01 M HCl (pH
the values of the k0 for the dopamine electrochemical reac- 2.10), 2.5 104 M DA, 5 mM SDS at dierent potential
tion (R1) were determined and are also reported in Table 3. scan rates, see Fig. 10, and their corresponding theoretical
For systems where strong adsorption of reactant and prod- CVs generated by non-linear tting Eq. (15) to the experi-
uct are involved, the full peak width at half-height mental data. From this gure it is concluded that the model
(EFWHM) should correspond to Eq. (8). From this equation on which is based, Eq. (9), can adequately describe the
and the experimentally measured EFWHM values, see Table experimental evidence and that when SDS is present in
3, the number of electrons transferred, n, in the electro- the system in concentrations grater that the CMC both,
chemical reaction was estimated, see Table 3. Once again, the oxidized and the reduced forms of DA, see (R1) are
it was found that dopamine oxidation, even in the presence strongly adsorbed. Notwithstanding, from the present
of SDS, corresponds to (R1) reaction. analysis it is possible to conclude that DG0ads;O < DG0ads;R .
Over again, it is conrmed that it is one the number of elec-
EFWHM 90:6=n 8 trons transferred, see Table 4.
 S. Corona-Avendano et al. / Journal of Electroanalytical Chemistry 609 (2007) 1726 25

50 60
of detector. It is possible to note that for [SDS] < CMC var-
40 50 50
ious products can be detected with dierent retention time
40

30 (tr), however, when [SDS] > CMC just one product was
i /A

30 30

20
20
10
detected at tR = 4 min. Considering the above, one may
10

0
conclude that this product should correspond to the semi-
10 0.3 0.35 0.4 0.45 0.5 0.55
quinone form of DA (DASQ), see reaction (R1). Li and
i / A

E/V
0 Christensen [38] have found from HPLC analysis, using
-10 an electrochemical detector, a 3 mm ODS column and a
-20 mixture of citrate buer (pH 3), EDTA and acetonitrile as
-30 the mobile phase, that DASQ was present at tR = 3.7 min.
-40 The product detected at tR = 2 min for [SDS] < CMC
should be related with that in reaction (R10).
-50
-500 -300 -100 100 300 500 700 900 1100 After the electrochemical and chromatographic studies
E / mV we can propose the following mechanisms of dopamine
Fig. 11. Comparison of an experimental CV () recorded in the system
electrochemical oxidation:
CPE/0.1 M NaCl, 0.01 M HCl (pH 2.1), 2.5 104 M DA, 5 mM SDS at In the absence of SDS in solution
40 mV s1 potential scan rate, see Fig. 10, and a theoretical CV (broken
line) generated by non-linear tting Eq. (15) to the experimental data. The
In this case the mechanism was an EC with a diusion
inset shows such a comparison for the anodic branch of CVs recorded at controlled not reversible electrochemical reaction (E)
the dierent potential scan rates indicated in the gure in mV s1. The best according to (R1) and a slow chemical reaction (C) in
t parameters are reported in Table 4. accordance with (R10).
In the presence of SDS in solution
 For [SDS] < CMC
Table 4
Best t parameters obtained by non-linear t of Eq. (15) to the anodic An EC mechanism with a diusion controlled reversible
branch of the CVs, in Fig. 10, recorded at dierent potential scan rates electrochemical reaction (E) according to (R1) and a chem-
v/mV s1 P1/lA P2 P3/V1 P4/V na ical reaction (C) in accordance with (R10).
 For [SDS] > CMC
10 50 1.29 44.46 0.47 1.1
30 120 10.58 43.60 0.52 1.1 An adsorption controlled electrochemical reaction (E)
40 160 0.53 43.67 0.45 1.1 according to (R1) where very likely both, the oxidized and
50 220 4.23 42.37 0.51 1.1 reduced forms of dopamine, are trapped into a SDS micelle
a
Calculated from parameter P3. which is strongly adsorbed onto the CPE surface. It is
important to note that these mechanisms involve the forma-
tion of a semiquinone free radical (DASQ). This molecule is
3.2.3. Chromatography study considered to be a highly reactive free radical. Recently,
Fig. 12 depicts the experimental chromatograms Terland et al. [48] have generated this product by one-elec-
obtained after imposing a macroelectrolysis to a DA aque- tron oxidation of dopamine using ferricyanide; they found,
ous solution containing dierent [SDS] and using two types by electron paramagnetic resonance spectroscopy a radical

Fig. 12. Experimental chromatograms recorded from an aqueous solution containing 104 M DA with dierent [SDS] after applying a dierent oxidation
potential, depending on the SDS concentration, to achieve the same current density for each solution during 5 min using dierent detector. (a)
Spectrophotometric, at constant wavelength (k = 480 nm) and (b) electrochemical, at constant potential (E = 315 mV).
26 S. Corona-Avendano et al. / Journal of Electroanalytical Chemistry 609 (2007) 1726
with g = 2.0045, formed by this oxidation, with relatively
long life (t1/2(obs) = 79 s at pH 6.5 and 25 C). Considering
our chromatographic results we can say that SDS can stabi-
lize DASQ during more than 4 min (retention time
observed), however, its life-time has not been estimated
yet.
4. Conclusions
From the results presented it is tting to conclude that in
the absence of SDS the DAs oxidationreduction mecha-
nism is given through reaction (R1), which involves forma-
tion of DASQ following a slow electrode kinetics, namely a
quasi-reversible process, that is diusion-controlled and
that has a slow chemical reaction coupled concerning the
DASQ cyclization (R10). As the [SDS] increases in the sys-
tem, when the [SDS] < CMC, it was found that the rate of
electron transfer kinetics (R1) increases, thus turning this
process from quasi-reversible to reversible. When the
[SDS] > CMC, the value of the heterogeneous standard
rate constant, k0, keeps increasing, and the process changes
from being mass transfer-controlled to one limited by
adsorption of the dopamine oxidized and reduced species.
From the chromatography results (electrochemical and
spectrophotometrical) it may be highlighted that the condi-
tion [SDS] > CMC gives rise to formation of only one oxi-
dation product corresponding to semiquinone (see (R1))
thus avoiding the coupled chemical reaction related to
cyclization of the DASQ (R10).
Acknowledgments
The authors acknowledge nancial support by CONA-
CYT. Also, G.A.-A. 184930 and S.C.-A. 58250 express
their gratitude to CONACyT for their postdoctoral fellow-
ships and Ph.D. grants. M.T.R.-S. and M.P.-P. thank
CONACyT for the support given through projects 46124
and 49775-Y (24658). Also G.A.R.-P., M.T.R.-S.,
M.A.R.-R., and M.P.-P. gratefully thank the SNI for the
distinction of their membership and the stipend received.
G.A.R.-P., M.A.R.-R. and M.P.-P. thank the Departa-
mento de Materiales, UAM-A, for the nancial support gi-
ven through projects 2260220, 2260231, 2260234. M.T.R.-S.
thanks PROMEP-PIFI-3 for supporting the Analytical
Chemistry Group, UAM-I-CA-33.
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